Radiation degradation of copolymers of methyl methacrylate and 3-oximino-2-butanone methacrylate

Copolymers of methyl methacrylate and 3-oximino-2-butanone methacrylate (OM) were investigated as deep-UV and e-beam resists. Their increased sensitivity relative to PMMA (up to 50 times) was correlated with the radiation chemical yields of the volatile products and main chain scissions. The degradation of these copolymers, activated by the 3-oximino-2-butanone entity, is discussed in terms of energy absorption mechanisms and the subsequent scission reactions.     

Gel permeation chromatography of branched polyethylene

The effect of long-chain branching must be considered in gel permeation chromatography to evaluate the molecular weight polydispersity of branched polyethylenes. Osmotic molecular weights of fractions of branched polyethylene were correlated with elution volumes; weight-average and number-average molecular weights of a branched polyethylene were determined. Molecular weight changes on crosslinking polyethylene by ionizing radiation are accompanied by branching and cannot be simply interpreted by gel permeation chromatography.     

Phenomena Affecting the Equilibrium of Al(III) and Zn(II) Extraction with Winsor II Microemulsions

The extraction of Al(III) and Zn(II) from an aqueous solution with two water-in-oil microemulsions, one containing di(2-ethylhexyl)phosphoric acid (DEHPA), was investigated to aid the understanding of the role of the extractant and the metal specific characteristics in the mechanism of microemulsion extraction. The extraction of Al with the DEHPA microemulsion increased by a factor of about 10 with respect to that in the conventional DEHPA system, whereas the extraction of Zn was lower than that in the single DEHPA system. Extraction with the DEHPA-free microemulsion was very low, showing that metal ion solubilization was not important in the mechanism of microemulsion extraction. It is proposed that the effect of the mixed microemulsion on the metal distribution coefficient is the result of the balance between a decrease in the complexation reaction yield due to the interaction between butanol and DEHPA, and the adsorption of the metal complex at the macro- and microinterfaces. The former leads to a decrease in Zn(II) extraction and the latter to Al(III) extraction synergism. Copyright 2000 Academic Press.     

Chemically-assisted fragmentation combined with multi-dimensional liquid chromatography and matrix-assisted laser desorption/ionization post source decay, matrix-assisted laser desorption/ionization tandem time-of flight or matrix-assisted laser desorption/ionization tandem mass spectrometry for improved sequencing of tryptic peptides

Derivatization of tryptic peptides using an Ettan CAF matrix-assisted laser desorption/ionization (MALDI) sequencing kit in combination with MALDI-post source decay (PSD) is a fast, accurate and convenient way to obtain de novo or confirmative peptide sequencing data. CAF (chemically assisted fragmentation) is based on solid-phase derivatization using a new class of water stable sulfonation agents, which strongly improves PSD analysis and simplifies the interpretation of acquired spectra. The derivatization is performed on solid supports, ZipTip(microC18, limiting the maximum peptide amount to 5 microg. By performing the derivatization in solution enabled the labeling of tryptic peptides derived from 100 microg of protein. To increase the number of peptides that could be sequenced, derivatized peptides were purified using multidimensional liquid chromatography (MDLC) prior to MALDI sequencing. Following the first dimension strong cation exchange (SCX) chromatography step, modified peptides were separated using reversed-phase chromatography (RPC). During the SCX clean up step, positively charged peptides are retained on the column while properly CAF-derivatized peptides (uncharged) are not. A moderately complex tryptic digest, prepared from six different proteins of equimolar amounts, was CAF-derivatized and purified by MDLC. Fractions from the second dimension nano RPC step were automatically sampled and on-line dispensed to MALDI sample plates and analyzed using MALDI mass spectrometry fragmentation techniques. All proteins in the derivatized protein mixture digest were readily identified using MALDI-PSD or MALDI tandem mass spectrometry (MS/MS). More than 40 peptides were unambiguously sequenced, representing a seven-fold increase in the number of sequenced peptides in comparison to when the CAF-derivatized protein mix digest was analyzed directly (no MDLC-separation) using MALDI-PSD. In conclusion, MDLC purification of CAF-derivatized peptides significantly increases the success rate for de novo and confirmative sequencing using various MALDI fragmentation techniques. This new approach is not only applicable to single protein digests but also to more complex digests and could, thus, be an alternative to electrospray ionization MS/MS for peptide sequencing.     

Gas-phase halonium metathesis and its competitors. Skeletal rearrangements of cationic adducts of saturated ketones

The methyl cation and CF(3)(+) attack saturated, acyclic ketones to make vibrationally excited adduct ions. Despite their high internal energies and short lifetimes, these adducts undergo deep-seated rearrangements that parallel slower processes in solution. Observed pathways include alkene and alkane expulsions, in addition to (in the case of CF(3)(+)) the precedented loss of CF(2)O + HF. For the vast majority of ketones, the principal charged products are the CF(3)(+) adducts of lighter carbonyl compounds, ions that are not easily prepared by other avenues. Evidence for ion structures comes from collisionally activated unimolecular decomposition and bimolecular ion-molecule reactions. Typical examples are di-n-propyl and diisopropyl ketones (both of which produce CH(3)CH=OCF(3)(+) as the principal ion-molecule reaction product) and pentamethylacetone (which produces (CH(3))(2)C=OCF(3)(+) as virtually the sole ion-molecule reaction product). Isotopic labeling experiments account for mechanisms, and DFT calculations provide a qualitative explanation for the relative abundances of products from unimolecular decompositions of the chemically activated CF(3)(+) adduct ions that are initially formed.     

Synthesis and complexation properties of poly(ethylene glycol)-linked mono- and bis-dioxocyclams

Both tri- and tetra(ethylene glycol) linked bis-chromium carbene complexes have been synthesized. These carbene complexes were photolyzed with N-protected imidazolines to give protected azapenams. These were transformed into polyether-linked basket dioxocyclams 4a,b and bis-dioxocyclams 5a,b. These compounds have cavities for the complexation of both "hard" and "soft" metal ions. The complexes of Ni, Ba, and Gd were synthesized.     

Countable spaces and common priors

We show that the no betting characterisation of the existence of common priors over finite type spaces extends only partially to improper priors in the countably infinite state space context: the existence of a common prior implies the absence of a bounded agreeable bet, and the absence of a common improper prior implies the existence of a bounded agreeable bet. However, a type space that lacks a common prior but has a common improper prior may or may not have a bounded agreeable bet. As a side-benefit of the proofs here, we also obtain a constructive proof of the no betting characterisation in finite spaces.     

Ammonia synthesis and decomposition on a Ru-based catalyst modeled by first-principles

A recently published first-principles model for the ammonia synthesis on an unpromoted Ru-based catalyst is extended to also describe ammonia decomposition. In addition, further analysis concerning trends in ammonia productivity, surface conditions during the reaction, and macro-properties, such as apparent activation energies and reaction orders are provided. All observed trends in activity are captured by the model and the absolute value of ammonia synthesis/decomposition productivity is predicted to within a factor of 1–100 depending on the experimental conditions. Moreover it is shown: (i) that small changes in the relative adsorption potential energies are sufficient to get a quantitative agreement between theory and experiment (Appendix A) and (ii) that it is possible to reproduce results from the first-principles model by a simple micro-kinetic model (Appendix B).