The adsorption of large proteins in electrofocusing on immobilized pH gradients: II. Dependence on the oligomeric state of Immobiline

Five proteins with molecular mass in excess of 200 kDa were found to adsorb onto gels during isoelectric focusing on immobilized pH gradients (IPGEF). To probe for the mechanism of that adsorption, the homogeneity of the six Immobiline preparations used to make IPGEF gels was tested. Five of these Immobiline preparations appear homogeneous in gel filtration of Sephadex G-10. The sixth Immobiline (pK 9.3) exhibits a minor component eluting ahead of the major peak and comprising less than 4% of the total Immobiline absorbing at 226 nm. The proportion of the minor component increases with column load. Major and minor components when isolated appear to equilibrate with one another. Judging by the results of mass spectrometry, all 6 preparations are free of small aggregates of less than 500-600 Da molecular mass. Ultrafiltration of the Immobiline preparations through a membrane with 500 Da nominal cutoff leads to partial desorption of only 3 of the 5 adsorbed proteins. CHAPS is ineffectual in desorbing the 5 proteins from the IPG gel made with ultrafiltered Immobilines. None of the 6 Immobiline preparations used precipitates ferritin. All large proteins that adsorb onto IPGEF gels in the pH range 4-9.5 also adsorb onto commercial IPGEF gels in the pH range 4-7.     

Synthesis and novel reactivity of halomethyldimethylsulfonium salts

Iodomethyl-, chloromethyl-, and fluoromethyldimethylsulfonium salts, 4b-d, have been synthesized and are observed to be highly reactive molecules that exhibit extraordinary diversity with respect to the nature of their reactivity, undergoing facile direct substitution (S(N)2) reactions, but also being highly susceptible to electron-transfer reactions. Cyclic voltametry experiments indicated that the iodomethyldimethylsulfonium compound, 4b, is a potent electron acceptor, even surpassing the reactivity of perfluoro-n-alkyl iodides in that capacity. The iodo- and chloromethyldimethylsulfonium salts, 4b,c, as well as the analogous iodomethyltrimethylammonium salt, 3a, are shown to be reactive SET acceptors.     

The application of neutron activation analysis to the determination of trace elements in pollen and sporopollenins

Neutron activation analysis has been used to assay the trace elements Co, Fe, Sc, Rb and Zn in pollen and derived sporopollenins. The method is capable of high precision and avoids the necessity for sample ashing and the introduction of reagent contamination. Rubidium was completely removed during the chemical isolation of sporopollenins and the remaining elements which survived chemical treatment were found in reduced amounts. The ratio of Sc: Fe in pollen and in several derived sporopollenins was found to be approximately constant. Results are discussed with reference to the possibilities of anomalous chemical behaviour of the elements resulting from irradiation.     

Bond breaking coupled with translation in rolling of covalently bound molecules

The response of a C60 molecule to manipulation across a surface displays a long range periodicity which corresponds to a rolling motion. A period of three or four lattice constants is observed and is accompanied by complex subharmonic structure due to molecular hops through a regular, repeating sequence of adsorption states. Combining experimental data and ab initio calculations, we show that this response corresponds to a rolling motion in which two of the four Si-C60 covalent bonds act as a pivot over which the molecule rotates while moving through one lattice constant and identify a sequence of C60 bonding configurations that accounts for the periodic structure.     

Modeling of high-frequency scattering from objects using a hybrid Kirchhoff/diffraction approach

In this paper a numerical discretization and transformation into the time domain of a hybrid Kirchhoff/diffraction method is presented for the modeling of high-frequency pulse scattering from rigid bodies. A series of benchmark cases, for smooth and rough spheres and cylinders, is presented to establish the accuracy of the method in the time domain.     

A molecular based scale for solvent basicity

The charge distribution on isolated polar molecules has been determined in the gas phase on the basis of the natural bond order (NBO) analysis. It is shown that the fractional negative charge on the heteroatom or atoms associated with solvent basicity is linearly correlated to popular empirical measures of this parameter in the liquid phase, namely, the solvent’s donor number, DN, and its solvatochromic basicity B _SC. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 1, pp. 32–38. The text was submitted by the authors in English.     

Fine-tuning of catalytic tin nanoparticles by the reverse micelle method for direct deposition of silicon nanowires by a plasma-enhanced chemical vapour technique

The reverse micelle method was used for the reduction of a tin (Sn) salt solution to produce metallic Sn nanoparticles ranging from 85 nm to 140 nm in diameter. The reverse micellar system used in this process was hexane-butanol-cetyl trimethylammonium bromide (CTAB). The diameters of the Sn nanoparticles were proportional to the concentration of the aqueous Sn salt solution. Thus, the size of the Sn nanoparticles can easily be controlled, enabling a simple, reproducible mechanism for the growth of silicon nanowires (SiNWs) using plasma-enhanced chemical vapour deposition (PECVD). Both the Sn nanoparticles and silicon nanowires were characterised using field-emission scanning electron microscopy (FE-SEM). Further characterisations of the SiNW's were made using transmission electron microscopy (TEM), atomic force microscopy (AFM) and Raman spectroscopy. In addition, dynamic light scattering (DLS) was used to investigate particle size distributions. This procedure demonstrates an economical route for manufacturing reproducible silicon nanowires using fine-tuned Sn nanoparticles for possible solar cell applications.