UV absorption spectra of HO2, CH3O2, C2H5O2, and CH3C(O)CH2O2 radicals and mechanism of the reactions of F and Cl atoms with CH3C(O)CH3

Pulse radiolysis techniques were used to measure the gas phase UV absorption spectra of the title peroxy radicals over the range 215–340 nm. By scaling to σ(CH₃O₂)_{240 nm} = (4.24 ± 0.27) × 10^?18, the following absorption cross sections were determined: σ(HO₂)_{240 nm} = 1.29 ± 0.16, σ(C₂H₅O₂)_{240 nm} = 4.71 ± 0.45, σ(CH₃C(O)CH₂O₂)_{240 nm} = 2.03 ± 0.22, σ(CH₃C(O)CH₂O₂)_{230 nm} = 2.94 ± 0.29, and σ(CH₃C(O)CH₂O₂)_{310 nm} = 1.31 ± 0.15 (base e, units of 10^?18 cm² molecule^?1). To support the UV measurements, FTIR‐smog chamber techniques were employed to investigate the reaction of F and Cl atoms with acetone. The F atom reaction proceeds via two channels: the major channel (92% ± 3%) gives CH₃C(O)CH₂ radicals and HF, while the minor channel (8% ± 1%) gives CH₃ radicals and CH₃C(O)F. The majority (>97%) of the Cl atom reaction proceeds via H atom abstraction to give CH₃C(O)CH₂ radicals. The results are discussed with respect to the literature data concerning the UV absorption spectra of CH₃C(O)CH₂O₂ and other peroxy radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 283–291, 2002     

Interaction of Metal–Dipeptide Complex with Ninhydrin in the Absence and Presence of Conventional CTAB Surfactant

The present work is aimed at studying the interaction between copper-glycyltyrosine [(Cu(II)-Gly-Tyr)]⁺ and ninhydrin in water and in micelles formed by cetyltrimethylammonium bromide (CTAB) using spectrophometric measurements at 80°C and pH 5.0. The order of reaction remains the same in the two systems, that is, first- and fractional-order kinetics with respect to [Cu(II)-Gly-Tyr]⁺ and [ninhydrin], respectively, in the excess of ninhydrin over [Cu(II)-Gly-Tyr]⁺. It was observed that the product formed is same in both the media. The reaction is catalyzed by CTAB, and the maximum rate enhancement is about three fold. Quantitative kinetic analysis of k_ψ–[CTAB] data was explained in terms of pseudo-phase of the micelles (assuming the association/incorporation of both the reactants at the micellar surface).     

Detection and quantized conductance of neutral atoms near a charged carbon nanotube

We describe a novel single atom detector that uses the high electric field surrounding a charged single-walled carbon nanotube to attract and subsequently field-ionize neutral atoms. A theoretical study of the field-ionization tunneling rates for atomic trajectories in the attractive potential near a nanowire shows that a broadly applicable, high spatial resolution, low-power, neutral-atom detector with nearly 100% efficiency is realizable with present-day technology. Calculations also show that the system can provide the first opportunity to study quantized conductance phenomena when detecting cold neutral atoms with mean velocities less than 15 m/s.     

Anomalous diffusion in living yeast cells

The viscoelastic properties of the cytoplasm of living yeast cells were investigated by studying the motion of lipid granules naturally occurring in the cytoplasm. A large frequency range of observation was obtained by a combination of video-based and laser-based tracking methods. At time scales from 10(-4) to 10(2) s, the granules typically perform subdiffusive motion with characteristics different from previous measurements in living cells. This subdiffusive behavior is thought to be due to the presence of polymer networks and membranous structures in the cytoplasm. Consistent with this hypothesis, we observe that the motion becomes less subdiffusive upon actin disruption.     

Synthesis and evaluation of new potential HIV-1 non-nucleoside reverse transcriptase inhibitors. New analogues of MKC-442 containing Michael acceptors in the C-6 position

Analogues of MKC-442 capable of undergoing Michael addition reactions were synthesised in order to investigate the activity against the HIV-1 mutant (Y181C). An improved activity was postulated on the basis of a possible covalent binding to the mercapto group of Cys181. Lithiation of the C-6 position of 1-ethoxymethyl-5-ethyl-1H-pyrimidine-2,4-dione (5) was followed by reaction with alpha,beta-unsaturated aldehydes and oxidation of the alcohols formed to give the alkenoyl analogues 1a-3a. Analogues 1b-3b containing an allyloxymethyl group in the N-1 position instead of the ethoxymethyl group could not be synthesised due to isomerisation of the allylic group during the metallation reaction. The NMR data for compounds 1a-3a showed a hindered rotation, which was more pronounced for the 6-cyclohexenylcarbonyl derivative 3a than for the propenyl derivatives 1a and 2a. Moderate activity against wild type HIV-1 was observed for the alcohol 8 and the ketones 2a-3a. However, no activity was observed against the Y181C mutant.     

Online variable-sized bin packing with conflicts

We study a new kind of online bin packing with conflicts, motivated by a problem arising when scheduling jobs on the Grid. In this bin packing problem, the set of items is given at the beginning, together with a set of conflicts on pairs of items. A conflict on a pair of items implies that they cannot be assigned to a common bin. The online scenario is realized as follows. Variable-sized bins arrive one by one, and items need to be assigned to each bin before the next bin arrives. We analyze the online problem as well as semi-online versions of it, which are the variant where the sizes of the arriving bins are monotonically non-increasing as well as the variant where they are monotonically non-decreasing.     

Determination of liposome–buffer distribution coefficients of charged drugs by capillary electrophoresis frontal analysis

The potential of using CE frontal analysis (CE‐FA) to study the interactions between a range of charged low molecular weight drug substances and liposomes was evaluated. The liposomes used were net negatively charged and consisted of 2‐oleoyl‐1‐palmitoyl‐sn‐glycero‐3‐phosphocholine and 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphate monosodium salt in a ratio of 80/20 mol%. Apparent distribution coefficients (D_mem), defined as the molar concentration of drug substance in the membrane phase divided by the molar concentration of drug substance in the aqueous phase, were successfully determined for six positively and eight negatively charged drug substances with log D_mem ranging from 1.35 to 3.63. The extent of liposome–buffer distribution was found to be dependent on the drug concentration. The results obtained with the developed CE‐FA method were in good agreement with results obtained by equilibrium dialysis. Furthermore, the CE‐FA method was faster, less labor intensive and required smaller sample volumes (～50 μL) compared with equilibrium dialysis. Thus, CE‐FA is an efficient and useful tool for the characterization of interactions between liposomes and low molecular weight drug substances.     

Heat-induced retrieval of immunogold labeling for nucleobindin and osteoadherin from Lowicryl sections of bone

The main purpose of this study was to examine whether antigens can be retrieved by heating Lowicryl sections of paraformaldehyde-fixed (PFF) tissues. Thus the intensity of the immunogold signal for two bone proteins (Nucleobindin (Nuc) and osteoadherin (OSAD)) was compared in retrieved and non-retrieved sections of PFF rat bone. As an additional experiment, the effect of antigen retrieval (for Nuc) in sections of tissue primary stabilized by high pressure freezing with subsequent freeze substitution (HPF-FS) was studied. Finally, the tissue distribution patterns of Nuc labeling were compared in non-retrieved HPF-FS sections to that of retrieved and non-retrieved PFF sections. Antigen retrieval in Lowicryl sections of PFF tissues showed significantly enhanced labeling intensity for both proteins in all compartments where they are known to occur. Retrieved PFF Lowicryl sections showed only minor ultrastructural differences compared to non-retrieved ones. Retrieval of HPF-FS sections exhibited no enhancement of labeling but rather a slight reduction, which was significant in the cytoplasm and in cartilage. Furthermore, striking ultrastructural differences were observed in retrieved HPF-FS sections compared to non-retrieved ones with loss of coherence and structure in sections subjected to heating. Comparison of the distribution patterns of Nuc in the sections of PFF and HPF-FS tissues showed discrepancy in most compartments. Antigen retrieval by heating Lowicryl sections of PFF tissues significantly enhances immunogold labeling in all cell compartments where the bone proteins are known to occur. However, the procedure may distort the tissue distribution pattern of bone proteins.