Epitaxial nucleation model for chiral-selective growth of single-walled carbon nanotubes on bimetallic catalyst surfaces

An epitaxial nucleation model for single-walled carbon nanotube (SWCNT) growth on bimetallic catalysts surfaces is reported in support of experimental observations of chiral enrichment. We model the bimetallic catalyst surfaces as a 2D (1 1 1) surface consisting of Ni or a combination of Ni and Fe atoms, with varying average bond length between nearest neighbor atoms which corresponds to the crystal structure of the alloys. The energies associated with nanotube cap formation on these various surfaces are calculated using density functional theory (DFT). We find that certain cap chiralities, such as (8, 4), are more stably bound to a surface that resembles a Ni_0.27Fe_0.73 bimetallic catalyst, whereas other chiralities, such as (9, 4), are more stable on a pure Ni surface. These results help explain the predominance of certain chiralities on specific bimetallic catalysts and provide a potential route to controlling the chirality of as-grown SWCNTs.     

Studies on phytosterol oxides. II: Content in some vegetable oils and in French fries prepared in these oils

Hydrogenated rapeseed oil/palm oil blend, sunflower oil and high-oleic sunflower oil, and French fries fried in these oils were assessed for contents of sterol oxidation products. Different oxidation products of phytosterols (7α- and 7β-hydroxy-sito-and campesterol, 7-ketosito- and 7-ketocampesterol, 5α,6α-epoxy-sito- and campesterol, 5β,6β-epoxy-sito-and campesterol, dihydroxysitosterol and dihydroxycampesterol) were identified and quantiated by gas chromatography (GC) and GC-mass spectroscopy. Rapeseed oil/palm oil blend contained 41 ppm total sterol oxides before frying operations. After two days of frying, this level was increased to 60 ppm. Sunflower oil and high-oleic sunflower oil had 40 and 46 ppm sterol oxides, respectively, before frying operations. After two days of frying operations, these levels increased to 57 and 56 ppm, respectively. In addition to campesterol and sitosterol oxidation products, small amounts of 7α- and 7β-hydroxystigmasterol were detected in the oil samples. Total sterol oxides in the lipids of French fries fried at 200°C in rapeseed oil/palm oil blend, sunflower oil, and high-oleic sunflower oil were 32, 37, and 54 ppm, respectively. The levels of total oxidized sterols, calculated per g sample, ranged from 2.4 to 4.0 ppm. In addition to the content of phytosterol oxides, full scan mass spectra of several oxidation products of stigmasterol are reported for the first time. Part of these results were presented at the 86th Annual Meeting of the AOCS, May 7–11, 1995, San Antonio, TX.     

Melt Rheological Behavior and Creep Response of EVA/TPU Blends: Exploring the Effect of Electron Beam Irradiation and Peroxide Cross-linking

The present study focuses on the variation of the melt rheological characteristics and the creep behavior of both electron beam-cross-linked and peroxide-cured ethylene vinyl acetate/thermoplastic polyurethane blends. The variation of complex viscosity, complex modulus, storage modulus, and loss modulus was evaluated over a wide range of frequency and strain amplitude using rubber process analyzer and the effect of radiation dose and peroxide concentration was investigated in detail. The creep study using dynamic mechanical analyzer shows that the creep behavior of the blends significantly improves after cross-linking and the creep compliance gradually decreases with the increasing radiation dose and peroxide content. An attempt was also made to pursue a comparative rheological and creep study among the peroxide-cured, electron beam-cross-linked and the coagent-treated dynamically vulcanized samples.     

Synthesis and characterization of solid-phase super acid catalysts and their application for isomerization of n-alkanes

In the present work, first, the reference catalyst super acidic nanostructured sulfated zirconia (SZ) and super acidic nanostructured aluminum chloride impregnated sulfated zirconium oxides in mole ratios of Zr⁴⁺:Al³⁺ as 2:1 (ACSZ-1), 1:1 (ACSZ-2), and 1:2 (ACSZ-3) were synthesized by a simple precipitation method. The catalytic performance of these four catalysts were evaluated during the isomerization of n-hexane, n-heptane, and n-octane to their corresponding branched chain isomers at low temperature and pressure conditions. ACSZ-2 shows high activity toward isomerization of n-hexane, n-heptane, and n-octane into their corresponding branched chain isomers. The reference catalyst SZ was proved to be less effective compare to the other three synthesized ACSZ catalysts. Ammonia-temperature-programmed desorption of these two materials ensures that the super acidity of ACSZ-2 is higher than that of SZ. Atomic force microscopic and scanning electron microscopic pictures predict the nature of the surface of the catalysts. Transmission electron micrographic analysis indicates the presence of particle-bulks having average size 12–20?nm, presenting an amorphous nature and having no definite surface morphology of ACSZ-2. Fourier transform infrared provides an outline regarding different linkages and bond connectivities between atoms and groups in ACSZ-2 and SZ. After catalyst evaluation and characterization a probable reaction mechanism has been proposed theoretically. The reactivity and selectivity of ACSZ-2 and SZ as well as the order and activation energy of the isomerization reactions in presence of ACSZ-2 have been calculated. The use of ACSZ-2 is beneficial from the point of cost efficiency as well as its use is energy saving.     

Pass-by-pass stress evolution in multipass welds

In multipass welding, each successive thermal cycle will introduce local melting, solid state phase transformations, grain growth, grain refinement, recrystallisation and recovery, all of which lead to a complicated stress state. Most stress measurements performed on multipass welded components represent the final residual stress state. Information concerning stress evolution on a pass-by-pass basis is difficult to find. In this investigation, six pass welds were made on high strength quenched and tempered steel sections, and depth resolved strain measurements in two orthogonal directions were carried out after each weld pass using energy dispersive synchrotron X-ray diffraction. The residual stresses were calculated using biaxial Hooke’s law. A thermal–metallurgical–mechanical welding model was constructed and validated with temperature and pass-by-pass stress measurements, which improves the reliability of the model. Cross-sectional stress distributions are presented after each pass, revealing the weld stress development in multipass welds.     

Laser surface alloying of aluminium with WC + Co + NiCr for improved wear resistance

In the present study, laser surface alloying of aluminium with WC + Co + NiCr (in the ratio of 70:15:15) has been conducted using a 5 kW continuous wave (CW) Nd:YAG laser (at a beam diameter of 0.003 m), with the output power ranging from 3 to 3.5 kW and scan speed from 0.012 m/s to 0.04 m/s by simultaneous feeding of precursor powder (at a flow rate of 1 × 10^− 5 kg/s) and using He shroud at a gas flow rate of 3 × 10^− 6 m³/s. The effect of laser power and scan speed on the characteristics (microstructures, phases and composition) and properties (wear and corrosion resistance) of the surface alloyed layer have been investigated in details. Laser surface alloying leads to development of fine grained aluminium with the dispersion of WC, W₂C, Al₄C₃, Al₉Co₂, Al₃Ni, Cr₂₃C₆, and Co₆W₆C. The microhardness of the alloyed zone is significantly improved to a maximum value of 650 VHN as compared to 22 VHN of the as-received aluminium substrate. The mechanism of microhardness enhancement has been established. The fretting wear behavior of the alloyed zone was evaluated against WC by Ball-on-disc wear testing unit and the mechanism of wear was established.     

Dicarbonylruthenium(II) complexes of diphosphine ligands and their catalytic activity

The hexa-coordinated chelate complexes of the type [Ru(CO)₂Cl₂(P-P)](1a,b) [where P-P = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene(a) and [bis(2-diphenylphosphinophenyl)ether(b)] have been synthesized by reacting the polymeric precursor [Ru(CO)₂Cl₂]_n with the ligands in 1:1 molar ratio. The complexes 1a,b are characterized by elemental analyses, Mass, IR and NMR spectroscopy together with the single crystal X-ray structure determination of 1a. The compound 1a crystallizes in a monoclinic system with space group C2/c showing a slightly distorted octahedral geometry around the Ru centre. The complexes 1a and 1b are thermally stable up to 300 °C and exhibit high catalytic activity in transfer hydrogenation of aldehyde and ketones to corresponding alcohols. The complexes 1a and 1b show much higher catalytic activity for the hydrogenation of aldehyde than ketones. In general, the catalytic efficiency of 1b is higher compared with 1a.     

Synthesis and Biological Characterization of (3R,4R)‐4‐(2‐(Benzhydryloxy)ethyl)‐1‐((R)‐2‐hydroxy‐2‐phenylethyl)‐piperidin‐3‐ol and Its Stereoisomers for Activity toward Monoamine Transporters

A novel series of optically active molecules based on a 4‐(2‐(benzhydryloxy)ethyl)‐1‐((R)‐2‐hydroxy‐2‐phenylethyl)‐piperidin‐3‐ol template were developed. Depending on stereochemistry, the compounds exhibit various degrees of affinity for three dopamine, serotonin, and norepinephrine transporters. These molecules have the potential for treating several neurological disorders such as drug abuse, depression, and attention deficit hyperactivity disorder.

     

Ultrafine particles from diesel vehicle emissions at different driving cycles induce differential vascular pro-inflammatory responses: Implication of chemical components and NF-κB signaling

Background

Nanometer silicon dioxide (nano-SiO₂) has a wide variety of applications in material sciences, engineering and medicine; however, the potential cell biological and proteomic effects of nano-SiO₂ exposure and the toxic mechanisms remain far from clear.

Results

Here, we evaluated the effects of amorphous nano-SiO₂ (15-nm, 30-nm SiO₂). on cellular viability, cell cycle, apoptosis and protein expression in HaCaT cells by using biochemical and morphological analysis, two-dimensional differential gel electrophoresis (2D-DIGE) as well as mass spectrometry (MS). We found that the cellular viability of HaCaT cells was significantly decreased in a dose-dependent manner after the treatment of nano-SiO₂ and micro-sized SiO₂ particles. The IC₅₀ value (50% concentration of inhibition) was associated with the size of SiO₂ particles. Exposure to nano-SiO₂ and micro-sized SiO₂ particles also induced apoptosis in HaCaT cells in a dose-dependent manner. Furthermore, the smaller SiO₂ particle size was, the higher apoptotic rate the cells underwent. The proteomic analysis revealed that 16 differentially expressed proteins were induced by SiO₂ exposure, and that the expression levels of the differentially expressed proteins were associated with the particle size. The 16 proteins were identified by MALDI-TOF-TOF-MS analysis and could be classified into 5 categories according to their functions. They include oxidative stress-associated proteins; cytoskeleton-associated proteins; molecular chaperones; energy metabolism-associated proteins; apoptosis and tumor-associated proteins.

Conclusions

These results showed that nano-SiO₂ exposure exerted toxic effects and altered protein expression in HaCaT cells. The data indicated the alterations of the proteins, such as the proteins associated with oxidative stress and apoptosis, could be involved in the toxic mechanisms of nano-SiO₂ exposure.     

Understanding the swelling of poly (N-isopropyl acrylamide) gels through the study of free volume hole size distributions using positron annihilation spectroscopy

Poly (N-isopropyl acrylamide) gels were prepared by UV polymerization with different degree of cross-linking in different solvents. Ethylene glycol dimethacrylate and penta-erythritol tetra-acrylate were used as cross-linkers, and methanol and dimethyl formamide (DMF) were used as solvents for gel preparation. The free volume fraction and hole size distribution in the dry gels were measured using positron annihilation lifetime spectroscopy. The equilibrium swelling of the samples in water was measured at room temperature. Both swelling properties of gels and the free volume distributions were seen to be sensitive to the amount, type, and functionality of cross-linkers as well as solvent medium used for synthesis. The gels prepared in DMF showed poor swelling properties than those prepared in methanol. The mean free volume hole size was higher while the variance of hole size distribution was smaller in the gels prepared in DMF medium compared to those prepared in methanol. The free volume fractions in the gels were found to be inversely correlated to the extent of equilibrium swelling for similar chemical compositions. The possible reasons are discussed.