Unprecedented Acid‐Promoted Polymerization and Gelation of Acrylamide: A Serendipitous Discovery

Dilute acid polymerizes degassed, aqueous acrylamide with concomitant gelation, without the need for added free radical initiator or cross‐linking agent. This reaction is accelerated by sonication or UV irradiation, but inhibited by adventitious oxygen or the addition of a free radical inhibitor, suggesting an acid‐accelerated free radical process. The resulting hydrogels are thixotropic in nature and partially disrupted by the addition of chaotropic agents, indicating the importance of hydrogen bonding to the 3D network. This discovery was made while trying to prepare pectin‐polyacrylamide hydrogels. We observed that pectin initiated the gelation of acrylamide, but only if the aqueous pectin samples had a pH lower than ca. 5.     

Lower functions for asymmetric Lévy processes

Summary Let {X _t } be a ¹ process with stationary independent increments and its Lévy measurev be given byv{yy>x}=x ^–L ₁ (x), v{yy<–x}=x ^–L ₂ (x) whereL ₁,L ₂ are slowly varying at 0 and and 0<1. We construct two types of a nondecreasing functionh(t) depending on 0<<1 or =1 such that lim inf a.s. ast 0 andt for some positive finite constantC.This research is partialy supported by a grant from Korea University     

Probe-induced native oxide decomposition and localized oxidation on 6H-SiC (0001) surface: an atomic force microscopy investigation

We report, for the first time, the native oxide decomposition/etching and direct local oxide growth on 6H-SiC (0001) surface induced by atomic force microscopy (AFM). Surface native oxide was decomposed and assembled into protruded lines when the negatively biased AFM tip was scanned over surface areas. The mechanism of decomposition was found to be governed by the Fowler-Nordheim emission current enhanced by the negatively biased AFM tip. Direct oxide growth on the SiC surface was achieved when the AFM tip was immobilized and longer bias duration applied. In particular, the aspect ratio of oxide grown on SiC was found to be several times higher than that on the Si surface. The improved aspect ratio on SiC was attributed to the anisotropic OH(-) diffusion involved in vertical and lateral oxidation along the polar and nonpolar directions such as [0001] and [110] axis in SiC crystal. The electron transport in the above AFM grown oxide on SiC was further investigated by I-V characteristics. The dielectrical strength of AFM oxide against degradation and breakdown under electrical stressing was evaluated.     

Side-chain radical losses from radical cations allows distinction of leucine and isoleucine residues in the isomeric peptides Gly-XXX-Arg

Sequencing of peptides via low-energy collision-induced dissociation of protonated peptides typically yields b(n) and y(n) sequence ions. The isomeric residues leucine and isoleucine rarely can be distinguished in these experiments since they give b(n) and y(n) sequence ions of the same m/z. Siu's pioneering work on electrospray ionization of copper complexes of peptides (Chu IK, Rodriquez CF, Lau TC, Hopkinson AC, Siu KWM. J. Phys. Chem. B 2000; 104: 3393) provides a way of forming radical cations of peptides in the gas phase. This method was used to generate M(+ small middle dot) ions of the two isomeric peptides Gly-Leu-Arg and Gly-Ile-Arg in order to compare their fragmentation reactions. Both radical cations fragment to give even electron y(2) and y(1) sequence ions as well as side-chain radical losses of CH(3) and CH(3)CH(2) for isoleucine and (CH(3))(2)CH for leucine. In contrast the [M + H](+) and [M + 2H](2+) ions do not allow distinction between the isomeric leucine and isoleucine peptides.     

Reactions of ruthenium benzylidenes with H2O to give benzaldehyde and (aqua)ruthenium complex

The second generation of Grubbs type catalyst, (PCy₃)(H₂IMes)Cl₂RuCHPh (1) undergoes the Cl replacement with CH₃CN to give cationic ruthenium carbene complexes, [(RCN)₃(H₂IMes)RuCHPh](OTf)₂ (2, R = CH₃ (a), Ph (b)) in the presence of AgOTf. The reaction of 2a with H₂O in the presence of CH₃CN gives (aqua)ruthenium complex, [Ru(H₂IMes)(NCCH₃) ₄(H₂O)](OTf)₂ (3) and benzaldehyde. Benzaldehyde is also observed in the reaction of 1 with H₂O. Plausible reaction pathways are suggested for the degradation of ruthenium benzylidenes to give benzaldehyde on the basis of the isotope labeling experiments.     

Palladium complexes of bidentate pyridine N‐heterocyclic carbenes: Optical resolution,antimicrobial and cytotoxicity studies

A series of bidentate pyridine‐functionalized palladium N‐heterocyclic carbene (Pd NHC) complexes with various wingtip substituents (R = methyl, phenyl and tert‐butyl) have been synthesized and evaluated for their potential biomedical applications as antimicrobials and antiproliferative drug candidates. The obtained Pd NHC complexes were applied in a standard broth microdilution assay for determination of their antimicrobial activities against thirteen strains of pathogenic microorganisms. In addition to that, cytotoxic activities of the Pd NHC complexes were also evaluated against three human cancer cell lines, namely breast (MCF‐7), colon (HCT116) and oral (H103) cancer cells, using a standard MTT assay. Upon coordination to palladium, the Pd NHC complexes show significant antimicrobial activities with minimum inhibitory concentrations in the micromolar range, and they are cytotoxic to the tested carcinomas with IC₅₀ ranging from 13 to 38 μM. Evidences for influence of both wingtip substituents and optical isomerism on the biological activities of the complexes have been found.