Optimization of oxidation of glycoproteins: an assay for predicting coupling to hydrazide chromatographic supports.

A rapid, simple assay for aldehydes generated by oxidation of saccharide units in glycoproteins, using dyes containing hydrazide functionalities, is described. The assay is used, in conjunction with tests of biological activity, to predict oxidation conditions that will result in a maximum of active protein coupled to a hydrazide chromatographic support. Glycoproteins are labeled with Lucifer Yellow CH or Texas Red Hydrazide, and the extent of labeling is determined. Using the assay, it is shown that the efficiency of coupling to Affi-Prep Hydrazide is proportional to oxidation.     

Rhodium chemzymes: Michaelis-Menten kinetics in dirhodium(II) carboxylate-catalyzed carbenoid reactions

Rhodium carboxylate-mediated reactions of diazoketones involving cyclopropanation, C-H insertion, and aromatic C-C double bond addition/electrocyclic ring opening obey saturation (Michaelis-Menten) kinetics. Axial ligands for rhodium, including aromatic hydrocarbons and Lewis bases such as nitriles, ethers, and ketones, inhibit these reactions by a mixed kinetic inhibition mechanism, meaning that they can bind both to the free catalyst and to the catalyst-substrate complex. Substrate inhibition can also be exhibited by diazocompounds bearing these groupings in addition to the diazo group. The analysis of inhibition shows that the active catalyst uses only one of its two coordination sites at a time for catalysis. Some ketones exhibit the interesting property that they selectively bind to the catalyst-substrate complex. The similarity of the kinetic constants from different types of reactions with similar diazoketones, regardless of the linking unit or the environment of the reacting alkene, suggests that the rate-determining step is the generation of the rhodium carbenoid. A very useful rhodium carboxylate catalyst for asymmetric synthesis, Rh(2)(DOSP)(4), shows slightly slower kinetic parameters than the achiral catalysts, implying that enantioselectivity of this catalyst is based on slowing reactions from one of the enantiotopic faces of the reactant, rather than any type of ligand-accelerated catalysis. A series of rhodium catalysts derived from acids with pK(a)s spanning 4 orders of magnitude give very similar kinetic constants.     

Identification of a novel series of alkylitaconic acids in wood cultures of Ceriporiopsis subvermispora by gas chromatography/mass spectrometry.

A novel series of long-chain unsaturated dicarboxylic acids consisting of a long aliphatic chain attached to the C-3 position of itaconic acid has been identified by gas chromatography/mass spectrometry during in vitro decay of eucalypt wood by the white-rot basidiomycete Ceriporiopsis subvermispora. The major compounds were identified as tetradecyl-, 7-hexadecenyl- and hexadecylitaconic acids by their mass fragmentation patterns. Other members of the same compound series, identified as dodecanyl-, tridecanyl-, tetradecenyl-, pentadecanyl-, octadecenyl- and octadecanylitaconic acids, were present in very minor amounts or traces. Whereas hexadecenylitaconic acid has already been reported in cultures of C. subvermispora, to our knowledge this is the first report of the presence of the other alkylitaconic acids in fungal cultures. These new alkylitaconic-type metabolites may constitute a source for peroxidizable lipids involved in lignin degradation during wood decay by C. subvermispora and other white-rot basidiomycetes.     

On the nature of point defects and the effect of oxidation on substitutional dopant diffusion in silicon

An extensive analysis of the substitutional dopant diffusion phenomena in silicon during oxidation is presented. The analysis covers qualitative as well as quantitative aspects of the oxidation-enhanced and -retarded diffusion (OED and ORD) phenomena, and examines three different possible assumptions that can be made on the nature of the silicon thermal equilibrium point defect species: silicon self-interstitials (I) only, vacancies (V) only, coexistence of I and V. The only consistent way to interpret all properly documented OED/ORD data is to assume that I and V coexist under oxidation as well as under thermal equilibrium conditions at high temperatures.     

Hydroacylation of 2-vinyl benzaldehyde systems: an efficient method for the synthesis of chiral 3-substituted indanones

Asymmetric rhodium-catalyzed hydroacylation has been utilized in the synthesis of 3-substituted indanones with high conversions and enantioselectivity. The hydroacylation reaction of 2-vinyl benzaldehyde had been previously reported to give a low yield of indanone and an unidentified product. We have identified this compound as a dimer of the starting material. Substitution at the alpha-position of the 2-vinyl benzaldehyde substrates blocks the competitive dimerization reaction and allows the reaction to proceed with yields generally greater than 90%. Utilization of BINAP as a chiral ligand results in good chemical yields and enantioselectivity greater than 95% in most cases.     

Novel hybrid mitigation strategy for improving the resiliency of hierarchical networks subjected to attacks

This paper studies the resiliency of hierarchical networks when subjected to random errors, static attacks, and cascade attacks. The performance is compared with existing Erdös–Rényi (ER) random networks and Barabasi and Albert (BA) scale-free networks using global efficiency as the common performance metric. The results show that critical infrastructures modeled as hierarchical networks are intrinsically efficient and are resilient to random errors, however they are more vulnerable to targeted attacks than scale-free networks. Based on the response dynamics to different attack models, we propose a novel hybrid mitigation strategy that combines discrete levels of critical node reinforcement with additional edge augmentation. The proposed modified topology takes advantage of the high initial efficiency of the hierarchical network while also making it resilient to attacks. Experimental results show that when the level of damage inflicted on a critical node is low, the node reinforcement strategy is more effective, and as the level of damage increases, the additional edge augmentation is highly effective in maintaining the overall network resiliency.