Sputtering of Langmuir-Blodgett multilayers by keV C60 projectiles as seen by computer simulations

Fundamental processes induced in a thick organic system composed of long, well-organized linear molecules by an impact of 5-20 keV C₆₀ are investigated. The organic system is represented by Langmuir-Blodgett multilayers formed from bariated molecules of arachidic acid. The thickness of the system varies between 2 and 16 nm. Coarse-grained molecular dynamics computer simulations are applied to investigate the energy transfer pathways and sputtering yields as a function of the kinetic energy of the projectile and the thickness of the organic overlayer.The results indicate that an impact of keV C₆₀ projectiles leads to significant ejection of organic material. The efficiency of desorption increases with the kinetic energy of the projectile for a given layer thickness. For a constant primary kinetic energy, the sputtering yield goes through a maximum and finally saturates as the LB layer becomes thicker. Such behaviour is caused by a competition between signal enhancement due to increasing number of organic molecules and signal decrease due to lowering of the amount of the primary energy being backreflected into the organic overlayer by the receding organic/metal interface as the layer is getting thicker. When the sample thickness becomes much larger than the penetration depth of the projectile, the sputtering yield is independent of thickness. The deposited energy is channelled by an open and ordered molecular structure, which leads to abnormally long projectile penetration and ion-induced damage.     

Reduction in thermal conductivity of Bi thin films with high-density ordered nanoscopic pores

We prepared two-dimensional Bi thin films with high-density ordered nanoscopic pores by e-beam evaporation of Bi metal. For this structure, we used polystyrene beads ranging from 200 to 750 nm in diameter as an etch mask. The typical hole and neck sizes of the Bi thin films with approximately 50 nm in thickness on SiO₂/Si substrates were in the range of 135 to 490 nm and 65 to 260 nm, respectively. By measuring the thermal characteristics through a 3ω technique, we found that the thermal conductivities of nanoporous Bi thin films are greatly suppressed compared with those of corresponding bulk materials. With a decrease in pore size to approximately 135 nm, the thermal conductivity decreased significantly to approximately 0.46 W/m·K at 300 K.     

Multi‐phosphorylation of the Intrinsically Disordered Unique Domain of c‐Src Studied by In‐Cell and Real‐Time NMR Spectroscopy

Intrinsically disordered regions (IDRs) are preferred sites for post‐translational modifications essential for regulating protein function. The enhanced local mobility of IDRs facilitates their observation by NMR spectroscopy in vivo. Phosphorylation events can occur at multiple sites and respond dynamically to changes in kinase–phosphatase networks. Here we used real‐time NMR spectroscopy to study the effect of kinases and phosphatases present in Xenopus oocytes and egg extracts on the phosphorylation state of the “unique domain” of c‐Src. We followed the phosphorylation of S17 in oocytes, and of S17, S69, and S75 in egg extracts by NMR spectroscopy, MS, and western blotting. Addition of specific kinase inhibitors showed that S75 and S69 are phosphorylated by CDKs (cyclin‐dependent kinases) differently from Cdk1. Moreover, although PKA (cAMP‐dependent protein kinase) can phosphorylate S17 in vitro, this was not the major S17 kinase in egg extracts. Changes in PKA activity affected the phosphorylation levels of CDK‐dependent sites, thus suggesting indirect effects of kinase–phosphatase networks. This study provides a proof‐of‐concept of the use of real‐time in vivo NMR spectroscopy to characterize kinase/phosphatase effects on intrinsically disordered regulatory domains.     

Synthesis of ω‐amino‐α‐phenylcarbonate alkanes and their polymerization to [n]‐polyurethanes

Aliphatic [n]‐polyurethanes have recently been synthesized from ω‐isocyanato‐α‐alkanols or, more traditionally, by cationic ring‐opening polymerization of cyclourethanes or by the Bu₂Sn(OMe)₂‐promoted polycondensation of ω‐hydroxy‐α‐O‐phenylurethane alkanes. For the latter procedures, the conditions employed do not seem to be suitable for highly functionalized monomers. In contrast, the polymerization of ω‐amino‐α‐phenylcarbonate alkanes is expected to occur under milder conditions. ω‐Amino‐α‐phenylcarbonate alkanes have been synthesized from 6‐aminohexanol (1) and 3‐aminopropanol (6). The procedure involves the N‐Boc protection of the amino group, followed by activation of the alcohol. Removal of the N‐Boc affords the corresponding ω‐amino‐1‐O‐phenyloxycarbonyloxyalkane hydrochlorides. Other oligomeric comonomers between 1 and 6 have been prepared. The polymerization of these precursors takes place in the absence of metal catalysts to afford the corresponding linear and regioregular [n]‐polyurethanes. The procedure described is useful for the preparation of stable ω‐amino‐α‐phenylcarbonate alkane derivatives, which possess varied chain lengths between the terminal functions. These monomers yield [n]‐polyurethanes having various structures starting from just two aminoalkanols. The polyurethanes were obtained in high yields, with reasonable molecular weight and polydispersity values, and they were characterized spectroscopically and thermally. These studies reveal constitutionally uniform structures that are free of carbonate or urea linkages. Copyright © 2010 Society of Chemical Industry     

Synthesis of PEGylated single wall carbon nanotubes by a photoinitiated graft from polymerization

A considerable amount of research has been devoted to carbon nanotubes because of their unique electrical, mechanical, optical, and chemical properties. Here, in this report, we introduce a novel, simple ultraviolet initiated “graft from” polymerization method to synthesize PEGylated carbon nanotubes. This grafting procedure significantly enhanced nanotube aqueous dispersibility and long term stability in solution. Mass of grafted polymer chains was easily modulated by adjusting polymerization reaction time, and nanomaterials containing up to 80% polymer by weight were synthesized. Nanotube morphology was characterized by SEM, TEM before and after the functionalization. In addition, the covalent bonding of polymer chains to the nanotubes structure was elucidated by Raman, ATR‐FTIR, and XPS spectroscopy. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Harnessing “Click”‐Type Chemistry for the Preparation of Novel Electronic Materials

Sequence‐independent or “click”‐type chemistry is applied for the preparation of novel π‐conjugated oligomers. A variety of bi‐functional monomers for Wittig–Horner olefination are developed and applied in a sequential protection–deprotection process for the preparation of structurally similar π‐conjugated oligomers. Selected oligomers are incorporated as the organic semiconductors in light‐emitting diodes and a field‐effect transistor, demonstrating the potential of the approach.     

Effect of cobalt promoter on Co–Mo–K/C catalysts used for mixed alcohol synthesis

The structures of sulfided Co–Mo–K/C catalysts were studied by means of X-ray diffraction (XRD), laser Raman spectra (LRS), and X-ray absorption fine structure (XAFS). Activities for alcohol synthesis via CO hydrogenation were used to characterize the catalytic performance of these catalysts. On the activated carbon support, molybdenum is mainly present as MoS₂ species which shrinks with the cobalt loading, while cobalt is mainly present in the form of “Co–Mo–S” phase at the low Co loading and partly in a Co₉S₈-like structure at higher Co loading. The catalysts exhibit outstanding performance for higher alcohol synthesis due to the addition of the promotion of cobalt. The activity for alcohol formation is optimized at a Co/Mo atomic ratio of 0.5. Co species operate as a synergistic system, rather than independently from the MoS₂ phase.     

Methionine restriction up‐regulates the expression of the pi class of glutathione S‐transferase partially via the extracellular signal‐regulated kinase‐activator protein‐1 signaling pathway initiated by glutathione depletion

Understanding the molecular events underlying gene regulation by amino acids has attracted increasing attention. Here, we explored whether the mechanism by which methionine restriction affects the expression of the π class of glutathione S‐transferase (GSTP) is related to oxidative stress initiated by glutathione (GSH) depletion. Rat primary hepatocytes were cultured in an L‐15‐based medium in the absence or presence of 200 μM L ‐buthionine sulfoximine (BSO) or in a methionine‐restricted L‐15 medium supplemented with 20 μM L ‐methionine up to 72 h. BSO and methionine restriction time‐dependently induced GSTP mRNA and protein expression in a similar pattern accompanied by a decrease in the cellular GSH level. The phosphorylation of extracellular signal‐regulated kinase (ERK), but not of c‐Jun NH₂‐terminal kinase and p38, was stimulated by methionine restriction and BSO. Electromobility gel shift assay showed that the DNA‐binding activity of nuclear activator protein‐1 (AP‐1) increased in cells exposed to methionine restriction or BSO. With the ERK inhibitor FR180204, AP‐1 activation and GSTP expression were abolished. Moreover, the induction of GSTP by methionine restriction and BSO was reversed by GSH monoethyl ester and N‐acetylcysteine. Our results suggest that methionine restriction up‐regulates GSTP gene expression, which appears to be initiated by the ERK‐AP‐1 signaling pathway through GSH depletion in rat hepatocytes.     

离散型状态观测器的分离合并解耦算法

在工程中经常使用状态观测器来观测不可直接获取的状态量以实现系统的反馈或前馈控制。本文提出了用广义逆矩阵来设计离散型状态观测器,并建议了一种新的算法,即分离合并介耦算法来设计组合观测器。该法计算简单,便于实现。使用本算法对直流调速系统构成转速负载组合观测器,以实现转速反馈控制和扰动前馈补偿。实验证明该算法是合理可行的,系统性能得到明显地改善。     

Influence of magnesium and aluminium ions on the copper a.c. deposition into aluminium anodic oxide film nanotubes

The influence of Mg²⁺ and Al³⁺ ions on a.c. deposition of copper nanowires into aluminium anodic oxide film (AOF) nanotubes has been studied using cyclic voltammetry and d.c. plasma emission spectrometry. From the analysis of copper quantities deposited into the Al AOF nanotubes (m _Cu), 0.02 M MgSO₄ concentration was found to be optimal for Cu(II) solutions. Moreover, it was shown that Mg²⁺ and Al³⁺ ions not only prevent the breakdown of the barrier layer of AOF, but change the rate of copper deposition and modify the shape of the m _Cu against pH plots depending on the a.c. voltage applied. From the analysis of the quantities of magnesium (m _Mg) incorporated into the Al AOF nanotubes, presumably in the form of Mg(OH)₂, the m _Mg against pH dependences were determined in MgSO₄ and MgSO₄ + CuSO₄ solutions. An increase in m _Mg from 30 g dm^–2 to 1 mg dm^–2 at pH 1.5 and from 6 g dm^–2 to 16 g dm^–2 at pH 7.0 was found under the same a.c. treatment conditions from MgSO₄ solutions without and with Cu²⁺ ions, respectively, indicating the incorporation of Mg(OH)₂ into the Al AOF nanotubes to be lower up to about one hundred times in the case of Cu deposition. Based on the experimental results, it was suggested that incorporation of the Mg(OH)₂ particles into the Al AOF nanotubes occurred simultaneously with growing copper nanowires under a.c. bias is insignificant, if the pH of the CuSO₄ + MgSO₄ solution is 2.5.