Metal Substitution in Layered Superconducting La2C2Br2

The effect of metal substitution in La₂C₂Br₂ by Lu (non-magnetic) and Ce (magnetic), respectively, on T_c was studied. The Lu substitution affects T_c, which decreases moderately with increasing amount of Lu. However Ce substitution affects T_c drastically, such that only 10% Ce substitution makes superconductivity disappear.     

5′-O-TBDMS-3′-O--(1H-Imidazole-1-Thiocarbonyl)thymidine: A Novel Intermediate for the Synthesis of 2,3′-Anhydrothymidine

Thermal or base-promoted conversion of 5′-O-TBDMS-3′-O-(1H-imidazole-1-thiocarbonyl)thymidine (1) afforded 5′-O-TBDMS-2,3′-anhydro-thymidine (2), a pivotal intermediate for the transformation of the 3′-hydroxy group of 2′-deoxyribonucleosides, in high yield.     

Palladium-Catalyzed Arylation and Vinylation of 2,3-Dihydrofuran with Hypervalent Iodonium Salts

The palladium-catalyzed arylation and vinylation of 2,3-dihydrofuran with aryl and alkenyl iodonium salts afforded 2-phenyl- or 2-alkenyl-2,5-dihydrofurans at room temperature in an aqueous medium.     

Dynamic identification of phosphopeptides using immobilized metal ion affinity chromatography enrichment, subsequent partial beta-elimination/chemical tagging and matrix-assisted laser desorption/ionization mass spectrometric analysis

The enrichment of phosphopeptides using immobilized metal ion affinity chromatography (IMAC) and subsequent mass spectrometric analysis is a powerful protocol for detecting phosphopeptides and analyzing their phosphorylation state. However, nonspecific binding peptides, such as acidic, nonphosphorylated peptides, often coelute and make analyses of mass spectra difficult. This study used a partial chemical tagging reaction of a phosphopeptide mixture, enriched by IMAC and contaminated with nonspecific binding peptides, following a modified beta-elimination/Michael addition method, and dynamic mass analysis of the resulting peptide pool. Mercaptoethanol was used as a chemical tag and nitrilotriacetic acid (NTA) immobilized on Sepharose beads was used for IMAC enrichment. The time-dependent dynamic mass analysis of the partially tagged reaction mixture detected intact phosphopeptides and their mercaptoethanol-tagged derivatives simultaneously by their mass difference (-20 Da for each phosphorylation site). The number of new peaks appearing with the mass shift gave the number of multiply phosphorylated sites in a phosphopeptide. Therefore, this partial chemical tagging/dynamic mass analysis method can be a powerful tool for rapid and efficient phosphopeptide identification and analysis of the phosphorylation state concurrently using only MS analysis data.     

Ortho alkylation of aromatic ketimine with functionalized alkene by Rh(I) catalyst

[reaction: see text] The reaction of the imine of aromatic ketones with functionalized alkenes was performed under a catalytic amount of (PPh3)3RhCl, and corresponding ortho-alkylated ketones were obtained after hydrolysis. A variety of functional groups in the alkene were tolerated in this ortho alkylation. This procedure expands the scope of ortho alkylation to the direct ortho functionalization of aromatic ketones.     

Patterned and controlled polyelectrolyte fractal growth and aggregations

Two-dimensional patterned and controlled polyelectrolyte aggregations (e.g., tree-like ramified structures) created by microcontact printing have been demonstrated and discussed. Polyelectrolyte-micropatterned aggregations on surfaces were controlled by the micropattern size and shape of PDMS stamps. The formation of aggregates was dependent on the ink and surface conditions, and the aggregates consisted of two distinct layers; strongly adsorbed, primary uniform layers and weakly adsorbed, secondary aggregation layers positioned on top of the primary layers. The adsorption of the primary layers was strong enough not to be washed away, while the aggregated secondary layers were easily removed by washing. The aggregation of secondary layers showed typical tree-like ramified structures of fractal growth and aggregation. Directional and confined stamping led to directing and confining the growth of the fractal polyelectrolyte clusters, respectively. The micropatterned primary uniform layers were not removed by extensive washing, and they were identified by selective nickel plating and charged particle selective adsorption in which the surface formed positive and negative micropatterns. These functional and patterned surfaces have great potentials for advanced devices and sensors.     

Refolding of Laccase in Dilution Additive Mode with Copper-Based Ionic Liquid

Ionic liquids (ILs) are molten salts which do not crystallize at room temperature. Tunable physicochemical properties of ILs including hydrophobicity and polarity facilitate their applications in many biological processes. In this study, a copper-based IL was employed in order to enhance the refolding efficiency of laccase from Trametes versicolor which requires copper as a cofactor. When 1-ethyl-3-methylimidazolium trichlorocuprate ([EMIM][CuCl₃]) was added to refolding buffer instead of urea, the laccase refolding yield was improved more than 2.7 times compared to the conventional refolding buffer which contains urea. When the refolding of laccase was carried out at different temperatures (4, 25, and 37 °C), the highest refolding yield was obtained at 25 °C. At low temperature, two conflicting effects, i.e., suppression of the aggregate formation and decrease of folding rate, influence the protein refolding. In contrast, a copper-based IL did not enhance the refolding of lysozyme, a non-copper-containing protein. From these results, we can conclude that this copper-based IL, [EMIM][CuCl₃], was exclusively effective on the refolding process of a copper-containing protein.     

Surface characteristics of Ti‐10Ta‐10Nb alloy modified by hydrogen peroxide treatment for dental implants

The use of titanium‐based alloys as biomaterials is becoming more common because they have a reduced elastic modulus, superior biocompatibility, specific strength, good corrosion resistance, superior strain control, and fatigue resistance compared to conventional stainless steel and Co? Cr alloys. However, when implanted into the human body these metals are problematic because they do not directly bond with living bone. Surface treatments play an important role in nucleating calcium phosphate deposition on a surgical titanium alloy implant. The purpose of this study is to examine whether the precipitation of apatite on Ti? 10Ta? 10Nb alloy is affected by surface modification in H₂O₂ solution. Specimens were chemically treated with a solution containing 30 wt% H₂O₂ at 80 °C for 1 h, and subsequently heat treated at 400 °C for 1 h. All specimens were immersed in SBF (Simulated Body Fluid) with a pH of 7.4 at 36.5 °C for seven days, and the surfaces were examined with XRD, SEM, EDX and in vitro testing. The microstructure analysis of the Ti? 10Ta? 10Nb alloy after etching with Keller's etchant showed a Widmanstatten pattern. The micro‐Vickers hardness number was 236.44 ± 4.99, and surface roughness was increased by the surface treatment. The wettability after surface treatment was better than on the nontreated surface. Resistance to cytotoxicity was decreased by the chemical surface treatment (P < 0.05). Copyright © 2011 John Wiley & Sons, Ltd.     

Simple, Rapid, and Sensitive Determination of Odorous Compounds in Water by GC–MS

A gas chromatographic–mass spectrometric method has been developed for rapid and sensitive determination of odorous compounds in water. The water sample (200 mL), at pH 6.5, was extracted with 1 mL pentane in a 250-mL separatory funnel. Fluorobenzene was added to the water sample as internal standard and the solution was mechanically shaken for 5 min and analyzed by GC–MS, with selected ion monitoring, without further concentration or purification steps. The peaks had good chromatographic properties and extraction of the compounds from water resulted in relatively high recoveries with small variations. The detection limits of the assay were 0.1 ng L^–1 for 2-isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, 2-methylisoborneol, and geosmin, 0.5 ng L^–1 for anisole, and 1.0 ng L^–1 for 2,4,6-trichloroanisole and trans, trans-2,4-heptadienal. Turn-around time was one day for up to approximately 40 samples. The method is simple, convenient, and can be learned easily by relatively inexperienced personnel. It was used to analyze seven odorous compounds in water from Decheung-Lake in Korea, and raw and treated water originating from the same lake. In the summer of 2001 significant levels of anisole (up to 225 ng L^–1) were observed, and geosmin and 2-methylisoborneol were detected at concentrations of up to 23.8 and 26.7 ng L^–1, respectively. 2-Isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, and trans, trans-2,4-heptadienal levels during that period were not significant. The method can used for simultaneous detection of several odorous compounds in water.