Radionuclides in the Kara sea bottom sediments

The contents and distribution of natural (214Pb, 214Bi, 228Ac, and 208Tl) and technogenic (90Sr, 137Cs, and 60Co) radionuclides in the Kara Sea bottom sediments was analyzed by using the materials collected by R/V "Pomor" (Murmansk Marine Biological Institute). In 1994, no high (critical) concentrations of technogenic radioisotopes were found in the sea sediments, while the spots (regions) of elevated 137Cs content found in 1984 were not confirmed in 1994. It was proposed that the main sources of entry of technogenic radionuclides in the sea sediments in the last years are the flow of the Ob'-Yenisei waters and container burials of radioactive waste in the sea, which appeared to have been markedly corroded. The latter is confirmed by detection in some places of 60Co, which was not previously found in the sediments.     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.     

A lysine to arginine substitution at position 146 of rabbit aldolase A changes the rate-determining step to Schiff base formation

Lys146 of rabbit aldolase A [D-fructose-1,6-bis(phosphate):D-glyceraldehyde-3-phosphate lyase, EC 4.1.2.13 [EC] ] was changedto arginine by site-directed mutagenesis. The k_cat of the resultingmutant protein, K146R, was 500 times slower than wild-type insteady-state kinetic assays for both cleavage and condensationof fructose-1,6-bis(phosphate), while the Km for this substratewas unchanged. Analysis of the rate of formation of catalyticintermediates showed K146R was significantly different fromthe wild-type enzyme and other enzymes mutated at this site.Single-turnover experiments using acid precipitation to trapthe Schiff base intermediate on the wild-type enzyme failedto show a build-up of this intermediate on K146R. However, K146Rretained the ability to form the Schiff base intermediate asshown by the significant amounts of Schiff base intermediatetrapped with NaBH₄. In the single-turnover experiments it appearedthat the Schiff base intermediate was converted to productsmore rapidly than it was produced. This suggested a maximalrate of Schiff base formation of 0.022 s^–1, which wasclose to the value of k_cat for this enzyme. This observationis strikingly different from the wild-type enzyme in which Schiffbase formation is >100 times faster than k_cat. For K146Rit appears that steps up to and including Schiff base formationare rate limiting for the catalytic reaction. The carbanionintermediate derived from either substrate or product, and theequilibrium concentrations of covalent enzyme-substrate intermediates,were much lower on K146R than on the wild-type enzyme. The greaterbulk of the guanidino moiety may destabilize the covalent enzyme-substrateintermediates, thereby slowing the rate of Schiff base formationsuch that it becomes rate limiting. The K146R mutant enzymeis significantly more active than other enzymes mutated at thissite, perhaps because it maintains a positively charged groupat an essential position in the active site or perhaps the Argfunctionally substitutes as a general acid/base catalyst inboth Schiff base formation and in subsequent abstraction ofthe C4-hydroxyl proton.     

Effects of pigmentation on siloxane–polyurethane coatings and their performance as fouling-release marine coatings

Siloxane–polyurethane paints were formulated and characterized for coating properties and performance as fouling-release (FR) marine coatings. Paints were formulated at 20 and 30 pigment volume concentrations with titanium dioxide, and aminopropyl-terminated poly(dimethylsiloxane) (APT-PDMS) loadings were varied from 0 to 30% based on binder mass. The coatings were characterized for water contact angle, surface energy (SE), gloss, and pseudobarnacle (PB) adhesion. The assessment of the FR performance compared with polyurethane (PU) and silicone standards through the use of laboratory biological assays was also performed. Biofilm retention and adhesion were conducted with the marine bacterium Cellulophaga lytica, and the microalgae diatom Navicula incerta. Live adult barnacle reattachment using Amphibalanus amphitrite was also performed. The pigmented coatings were found to have properties and FR performance similar to those prepared without pigment. However, a higher loading of PDMS was required, in some cases, to obtain the same properties as coatings prepared without pigment. These coatings rely on a self-stratification mechanism to bring the PDMS to the coating surface. The slight reduction in water contact angle (WCA) and increase in pseudobarnacle release force with pigmentation suggests that pigmentation slowed or interfered with the self-stratification mechanism. However, increasing the PDMS loading is an apparent method for overcoming this issue, allowing for coatings having similar properties as those of clear coatings and FR performance similar to those of silicone standard coatings.     

Enhancing compatibilizer function by controlled distribution in hydrophobic polylactic acid/hydrophilic starch blends

Various polylactic acid (PLA)/cornstarch blends, with and without the compatibilizer methylenediphenyl diisocyanate (MDI), were prepared by melt processing using a twin‐screw extruder. In the blends where it was included, MDI was distributed in either the PLA or starch phase through controlling processes conditions. The effects of MDI inclusion and its distribution on the resultant microstructures, mechanical properties, and thermal and rheological behaviors of the blends were studied via scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, mechanical testing, and Haake rheometer. The results showed that when the MDI was distributed in the starch phase before blending with PLA, the highly reactive isocyanate groups in the MDI were most probably consumed by water, resulting in an overall weakening of its compatibilizing effect. However, when the MDI was distributed in the PLA phase before blending with starch, modulus, yield strength, and impact strength were all increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

油-气管道检测机器人技术现状及展望

为提高油-气管道检测的效果,结合国内外典型管道机器人的特点,综合分析了管道机器人运动控制技术、定位技术和实时检测技术3个方面的现状,并指出了核心技术的不足;针对石油化工行业高温带压管道环境,提出管道检测机器人的研究重点为分层模糊神经网络运动控制技术、CCD视觉定位技术、低频电磁定位技术和分层图像分割的优化方法等。为进一步提高化工油-气管道内检测机器人的检测效果提供了理论依据。     

Insight into the Mechanism of Phenylacetate Decarboxylase (PhdB), a Toluene-Producing Glycyl Radical Enzyme

We recently reported the discovery of phenylacetate decarboxylase (PhdB), representing one of only ten glycyl-radical-enzyme reaction types known, and a promising biotechnological tool for first-time biochemical synthesis of toluene from renewable resources. Here, we used experimental and computational data to evaluate the plausibility of three candidate PhdB mechanisms, involving either attack at the phenylacetate methylene carbon or carboxyl group [via H-atom abstraction from COOH or single-electron oxidation of COO⁻ (Kolbe-type decarboxylation)]. In vitro experimental data included assays with F-labeled phenylacetate, kinetic studies, and tests with site-directed PhdB mutants; computational data involved estimation of reaction energetics using density functional theory (DFT). The DFT results indicated that all three mechanisms are thermodynamically challenging (beyond the range of many known enzymes in terms of endergonicity or activation energy barrier), reflecting the formidable demands on PhdB for catalysis of this reaction. Evidence that PhdB was able to bind α,α-difluorophenylacetate but was unable to catalyze its decarboxylation supported the enzyme's abstraction of a methylene H atom. Diminished activity of H327A and Y691F mutants was consistent with proposed proton donor roles for His327 and Tyr691. Collectively, these and other data most strongly support PhdB attack at the methylene carbon.     

Polyampholyte acrylic latexes for tablet coating applications

Polyampholyte latexes can exist within a certain pH range as low‐viscosity aqueous dispersions, while upon a pH shift to the vicinity of the isoelectric point they undergo ionic coacervation. Three classes of coacervation latexes were synthesized and evaluated for their suitability for use in tablet coating applications. Pharmaceutical tablet coatings are commonly based on hydroxypropyl methyl cellulose, poly(vinyl alcohol), and acrylic polymers. Because of the high viscosity of their aqueous solutions, and to the consequent required low concentrations of the tablet coating polymers in the coating solutions to enable sufficiently low viscosity for effective spray application, the current commercial pharmaceutical tablet coating technology requires the removal of large amounts of water during the manufacturing process. In this work, films prepared from high‐solids, low‐viscosity coacervated acrylic latexes showed good hardness, very low tackiness, an excellent combination of optical properties, and very low water vapor permeability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40049.