Suzuki cross-coupling reactions using reverse-phase glass beads in aqueous media

Reverse-phase glass beads have been employed in Suzuki reactions to provide, in aqueous media, a route to diverse polar substrates in good yield and with low levels of palladium leaching.     

Buckling delamination in compressed multilayers on curved substrates with accompanying ridge cracks

Residually compressed films and coatings are susceptible to buckle delamination. The buckles often have linear or telephone cord morphology. When the films are brittle, such buckles are susceptible to the formation of ridge cracks that extend along their length, terminating close to the propagating front. The ridge-cracked buckles are invariably straight-sided (not telephone cord) and differ in width. Buckle delaminations of this type occur on flat and curved substrates: having greatest technological relevance in the latter. They occur not only in single layer films but also in multilayers, such as thermal barrier systems. Establishing the mechanics of ridge-cracked buckle delaminations for multilayers on curved substrates serves two purposes. (a) It allows the prediction of buckle delamination and spalling for technologically important systems. (b) It provides a test protocol for measuring properties such as the delamination toughness of the interface and the stresses in the layers. Both objectives are addressed in the article: the latter by devising an inverse algorithm. Implementation of the algorithm is demonstrated for diamond-like carbon films on planar glass substrates and a thermal barrier multilayer on a curved superalloy substrate.     

Steady-State Kinetics of Aminopeptidase Catalysis: A Stopped-Flow Radiationless Energy Transfer Study

Stopped-flow radiationless energy transfer experiments have been carried out to investigate the hydrolysis of some dansyl peptide substrates (S) catalyzed by aminopeptidase (E). RET between enzyme tryptophanyl residues and the dansyl group in the substrate allowed direct observation and quantitation of the enzyme-substrate (ES) complexes. Analysis of the stopped-flow RET traces gives k_cat = 1.32 s^?1 and K_M = 47 μM for Leu-Ala-NH(CH₂)₂NH-Dns (Leu-Ala-DED) and k_cat = 4.80 s^?1 and K_M = 196 μM for Leu-Gly-NH(CH₂)₂NH-Dns (Leu-Gly-DED). The activation energies of the enzymatic reactions were determined from the Arrhenius plots to be 57 and 38 kJ mol^?1 for Leu-Ala-DED and Leu-Gly-DED, respectively. The kinetic results indicate that the enzyme binds Leu-Ala-DED more tightly than Leu-Gly-DED as revealed by a small value of K_M. That this enzyme catalyzes the turnover of Leu-Gly-DED more efficiently than Leu-Ala-DED is reflected in a large value of k_cat and a small activation energy. The RET signals during the hydrolysis of Leu-Val-NH(CH₂)₂NH-Dns were extremely weak probably because of the inefficient energy transfer in the ES complex or the retention of the product in the enzyme after completion of the reaction. Aminopeptidase was inactive towards the dansyl compounds of the single amino acid studied. This fact may be due to an unfavorable conformation of these compounds in the ES complexes (small k_cat) or a weak binding of the substrates to the enzyme (large K_M) or both.     

Development of cube textured Ni–5 at.%W alloy substrates for coated conductor application using a melting process

Biaxially textured Ni–5 at.%W substrates have been prepared by cold rolling, followed by three different annealing routes. In this paper, the processes of melting Ni and W metals, flat rolling, various annealing methods are described in detail. The Ni–5 at.%W tapes annealed under either high vacuum or flowing Ar (7% H₂) gas were characterized by X-ray pole figures, ODF, EBSD as well as AFM analysis. The texture analysis indicated that as fabricated tapes have a sharp cube texture formed after annealing at a wide temperature range of 800–1100 °C. The high quality of cube orientation on tapes was obtained after a two-step annealing (TSA), where the percentage of the cube texture component was as high as 93.5% within a misorientation angle smaller than 8° from EBSD analysis. Furthermore, it was also observed that the number of twin boundaries in this tape decreased with respect to that of tapes annealed both in vacuum and one-step gas annealing. From AFM on 1 μm² areas, it was concluded that the roughness (RMS) on the tape surface reached 0.98 nm.     

Synthesis and characterization of surface‐initiated polymer brushes on silicon substrates by reversible addition fragmentation chain transfer polymerization

Polymer brushes were prepared by using the reversible addition fragmentation chain transfer (RAFT) technique. The silicon substrates (Si (111) surface) were modified with ethyl xanthate groups which were introduced by the treatment of Si (111) surface with sodium ethyl xanthate. The polymer brushes were then prepared under RAFT conditions from the Si (111) wafer. Its “living” characteristics were determined by a series of characterizations including gel permeation chromatography (GPC), ellipsometry, and contact angle measurements. The results showed a well‐defined graft layer consisting of polymer brushes with low‐polydispersity could be prepared directly on Si (111)‐X surface (where X represents an ethyl xanthate groups). The structure of the polymer brushes was characterized and confirmed with the surface sensitive techniques such as X‐ray photoelectron spectroscopy (XPS) and scanning probe microscopy (SPM). Copyright © 2007 John Wiley & Sons, Ltd.     

Originalarbeiten: Radiogaschromatographische Untersuchungen an flüchtigen Photolyseprodukten des Systems Bis-(tributylzinn)-oxid-(butyl-1-14C)/Cellulose

Es werden Apparatur und Methode zur radiogaschromatographischen Trennung und Identifizierung von Photolyseprodukten des Systems Bis-(tributylzinn)-oxid-(butyl-1-¹⁴C)/Cellulose beschrieben. Dabei wurde nachgewiesen, daβ beim UV-induzierten Abbau dieses Systems u. a. n-Butan-¹⁴C und n-Octan-¹⁴C gebildet werden. Die von der Organozinnverbindung abgespaltenen ¹⁴C-markierten Butylradikale stabilisieren sich demnach durch Reaktion mit Wasserstoffatomen ( Photolyseprodkt der Cellulose) und durch Dimerisierung.     

氩、氢混合等离子体处理对GaAs表面性质及发光特性的影响

介绍了一种氩、氢混合等离子体清洗GaAs基片的实验工艺,深入研究了氩、氢等离子体清洗GaAs表面污染物和氧化层,并活化表面性能的基本原理,同时讨论了气体流量、溅射功率和清洗时间等不同溅射参数对等离子体清洗效果的影响。结果表明,在氩气和氢气流量分别为10 cm³/min和30 cm³/min,溅射功率为20 W,清洗时间为15 min的条件下,GaAs样品的光致发光强度提高达139.12%,样品表面的As-O键和Ga-O键基本消失。     

Structural transition of secondary phase oxide nanorods in epitaxial YBa2Cu3O7−δ films on vicinal substrates

A theoretical study of a structural transition of secondary phase oxide nanorods in epitaxial YBa₂Cu₃O_7?δ films on vicinal SrTiO₃ substrates is presented. Two possible types of film/substrate interface are considered, with one assuming complete coherence, while the other is defective as manifested by the presence of antiphase grain boundaries. Only in the former case does the increase of the vicinal angle of the substrate lead to a substantial change of the strain field in the film, resulting in a transition of the nanorod orientation from the normal to the in-plane direction of the film. The calculated threshold vicinal angle for the onset of the transition and lattice deformation of the YBa₂Cu₃O_7?δ film due to the inclusion of the nanorods is in very good agreement with experimental observations. This result sheds lights on the understanding of the role of the film/substrate lattice mismatch in controlling self-assembly of dopant nanostructures in matrix films.     

Elimination of GeO2 and Ge3N4 interfacial transition regions and defects at n-type Ge interfaces: A pathway for formation of n-MOS devices on Ge substrates

The contribution from relatively low-K SiON interfacial transition regions (ITRs) between Si and transition metal (TM) gate dielectrics places a significant limitation on equivalent oxide thickness (EOT) scaling for Si complementary metal-oxide-semiconductor (CMOS) devices. This limitation is equally significant and limiting for Ge CMOS devices. Low-K Ge-based ITRs in Ge devices have also been shown to limit performance and reliability, particular for n-MOS field effect transistors. This article identifies the source of significant electron trapping at interfaces between n-Ge or inverted p-Ge, and Ge oxide, nitride and oxynitride ITRs. This is shown to be an interfacial band alignment issue in which native Ge ITRs have conduction band offset energies smaller than those of TM dielectrics, and trap electrons for negative Ge substrate bias. This article also describes a novel remote plasma processing approach for effectively eliminating any significant native Ge ITRs and using a plasma-processing/annealing process sequence for bonding TM gate dielectrics directly to the Ge substrate surface.     

Efficient immobilization of silver nanoparticles on metal substrates through various thiol molecules to utilize a gap mode in surface enhanced Raman scattering

To utilize a gap mode in surface enhanced Raman scattering, we elucidated the interaction between adsorbed species and Ag nanoparticles (AgNPs). Various thiol molecules such as normal alkanethiols, thiols with a phenyl, cyclohexane or naphthalene ring on Ag films immobilized AgNPs through van der Waals force, and electrostatic interaction. Immobilized AgNPs provided enormous Raman enhancement by a factor of 10⁷–10¹⁰ for thiol molecules at a nanogap, in consistent with that anticipated by finite difference time domain calculations. Only alkanethiols with a tert-methyl group and those with a carboxylic group did not immobilize any AgNPs probably owing to steric hindrance. A gap mode is relevant for a variety of metals even with large damping like Pt and Fe, indicating a crucial role of electric multipoles in AgNPs generated by a localized surface plasmon and induced mirror images in metal substrates for markedly enhanced electric field at a nanogap.