Using colloid lithography to fabricate silicon nanopillar arrays on silicon substrates

In this study, we partially grafted geminal silanol groups in the protecting organic shells on the surfaces of gold nanoparticles (AuNPs) and then assembled the alkyl-AuNP-Si(OH)(4) particles onto the surfaces of silicon (Si) wafers. The density of assembled AuNPs on the Si surface was adjusted by varying the geminal silanol group content on the AuNP surface; at its optimal content, it approached the high assembly density (0.0254 particles/nm(2)) of an AuNP assembled monolayer. Using reactive-ion etching (RIE) with the templates as masks, we transferred the patterned AuNP assemblies to form large-area, size-tunable, Si nanopillar arrays, the assembly density of which was controlled by the dimensions of the AuNPs. Using this colloidal lithography (CL) process, we could generate Si nanopillars having sub-10-nm diameters and high aspect ratios. The water contact angles of the high-aspect-ratio Si nanopillars approached 150°. We used another fabrication process, involving electron beam lithography and oxygen plasma treatment, to generate hydrophilic 200-nm-resolution line patterns on a Si surface to assemble the AuNPs into 200-nm-resolution dense lines for use as an etching mask. Subsequent CL provided a patterned Si nanopillar array having a feature size of 200 nm on the Si surface. Using this approach, it was possible to pattern sub-10-nm Si nanopillar arrays having densities as high as 0.0232 nm(-2).     

Radiation induced preparation of new multifunctional nanobiowebs

New poly(vinylidene fluoride) based multi-functional (electroconductive, bioactive and catalytic) nano-biowebs were prepared through gamma radiation induced formation of silica and gold nanoparticles (Au NPs) within electrospun (poly vinylidene fluoride) nanofiberous membranes. The multifunctional membrane is designated as PVdF@silica/Au ESNFM. The morphology of PVdF@silica/Au ESNFM was examined by field emission scanning electron microscopy. The presence of Au particles was confirmed by energy dispersive x-ray analysis. The crystal structure of Au particles and the formation of silica were confirmed by X-ray diffraction analysis. The multi-functionalities (electroconductive, bioactive and catalytic) of the nano-webs were evaluated by cyclic voltammetry. Cytochrome c was immobilized to generate nano-bioweb (PVdF@silica/Au/cyt c ESNFM), which exhibited electrochemical responses to nitrite ions.     

Decreased Human Platelet Activation and Mouse Pulmonary Thrombosis by Rutaecarpine and Comparison of the Relative Effectiveness with BAY11-7082: Crucial Signals of p38-NF-κB

Platelets play a critical role in arterial thrombosis. Rutaecarpine (RUT) was purified from Tetradium ruticarpum, a well-known Chinese medicine. This study examined the relative activity of RUT with NF-κB inhibitors in human platelets. BAY11-7082 (an inhibitor of IκB kinase [IKK]), Ro106-9920 (an inhibitor of proteasomes), and RUT concentration-dependently (1–6 μM) inhibited platelet aggregation and P-selectin expression. RUT was found to have a similar effect to that of BAY11-7082; however, it exhibits more effectiveness than Ro106-9920. RUT suppresses the NF-κB pathway as it inhibits IKK, IκBα, and p65 phosphorylation and reverses IκBα degradation in activated platelets. This study also investigated the role of p38 and NF-κB in cell signaling events and found that SB203580 (an inhibitor of p38) markedly reduced p38, IKK, and p65 phosphorylation and reversed IκBα degradation as well as p65 activation in a confocal microscope, whereas BAY11-7082 had no effects in p38 phosphorylation. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay shows that RUT and BAY11-7082 did not exhibit free radical scavenging activity. In the in vivo study, compared with BAY11-7082, RUT more effectively reduced mortality in adenosine diphosphate (ADP)-induced acute pulmonary thromboembolism without affecting the bleeding time. In conclusion, a distinctive pathway of p38-mediated NF-κB activation may involve RUT-mediated antiplatelet activation, and RUT could act as a strong prophylactic or therapeutic drug for cardiovascular diseases.     

Novel acid-catalyzed rearrangement of methanofullerenes bearing an alpha-ylidic ester to cyclopentanofullerenes: a vinyl cyclopropane-type ring expansion

A novel acid-catalyzed ring expansion of methanofullerenes bearing an alpha-ylidic ester has been investigated. Treatment of dialkyl acetylenedicarboxylate and tricycloalkylphosphine with C(60) led to the isolation of a methanofullerene ylide after passing the reaction mixtures through a basic alumina column. If the reaction mixture was passed through a silica gel column, a cyclopentanofullerene was isolated instead. These new cyclopentanofullerenes consisted of a fused cyclopentanone ring bearing an alpha-hydroxy ester and a phosphonium ylide and were confirmed by their NMR, mass, and X-ray diffraction data. The cyclopentanofullerenes were formed by the ring expansion of the corresponding methanofullerenes in the presence of silica gel. The ring expansion also proceeded by treating methanofullerene with acetic acid in chloroform. On the other hand, the methanofullerenes from RO(2)CCCCO(2)R, PAr(3), and C(60) were stable in silica gel. However, upon heating with acetic acid at 50 degrees C, they underwent ring expansion and dephosphination to give cyclopentenofullerenes. An implicit vinyl cyclopropane ring expansion mechanism was proposed to account for this novel acid-catalyzed rearrangement.     

On the asymptotic behavior of expanding gradient Ricci solitons

Let (M, g, f) be an n-dimensional expanding gradient Ricci soliton with faster-than-quadratic-decay curvature, i.e., ${\lim_{{\rm dist}(O,x)\rightarrow\infty} |{\rm Sect}(x)|\cdot {\rm dist}(O,x)^2=0}$ . When M is simply connected at infinity and n??? 3, we show that its tangent cone at infinity must be a manifold and is isometric to ${\mathbb{R}^n}$ . Here, we also assume that M has only one end for the simplicity of the statement. A crucial step to gain the regularity of the tangent cone at infinity is to prove that the injectivity radius grows linearly. This can be achieved by combining the curvature assumption and a lower bound estimate of volume ratio of all geodesic balls, which is attained as Theorem 3. On the other hand, we also study the asymptotic volume ratio of non-steady gradient Ricci solitons under other weaker conditions.     

Potentialfeld- und Kraftkonstanten voncis- undtrans-Difluordiazin

Zusammenfassung Ancis-Difluordiazin planarer Konfiguration mit C_2v-Symmetrie und antrans-Difluordiazin planarer Konfiguration mit zentrosymmetrischer Struktur mit C_2h-Symmetrie wurde eine Schwingungs- und Strukturanalyse unter Verwendung eines modifizierten Valenzkraftfeldes mit sechs Kraftkonstanten ausgeführt. Die Berechnung der Kraftkonstanten erfolgte nach gruppentheoretischen Methoden auf der Grundlage der Ergebnisse neuerer Struktur- und verfeinerter Schwingungsanalysen. Die Ergebnisse werden mit den an Molekülen mit ähnlichen chemischen Bindungen und angenähert identischen Kernabständen erhobenen verglichen.

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Potential field and force constants of cis- and trans-difluorodiazines

Vibrational and structural analysis ofcis-difluorodiazine possessing a planar configuration with C_2v symmetry and oftrans-difluorodiazine possessing a planar configuration of centrosymmetrical structure with C_2h symmetry has briefly been made. A modified six-force constant valence force field has been employed and the force constants have been evaluated from the recent structural and refined vibrational data for bothcis- andtrans-difluorodiazines by the group theoretical method. A brief discussion of the results has been made in relation to other molecules having similar chemical bonds with nearly identical internuclear distances.

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Mit 2 Abbildungen     

Electrochemical mass spectroscopic and surface photovoltage studies of catalytic water photooxidation by undoped and carbon-doped titania

Carbon-doped TiO2, demonstrated as an efficient photocatalyst in visible light photooxidation of organic compounds, was prepared with different doping concentrations and investigated via differential electrochemical mass spectroscopy (DEMS) and capacitive surface photovoltage (SPV) measurements in the form of thin layer electrodes. In all cases the total photocurrent as well as the surface photovoltage of the doped materials decreased markedly in relation to the undoped one. No detectable oxygen evolved from the doped electrodes in acidic solution under UV-light excitation. Since an oxidation of formic acid is still apparent, it is concluded that this oxidation occurs via isolated, catalytically poorly active trap states within the forbidden energy region. The existence of these states is confirmed by capacitive SPV measurements.     

Solid-state molecular folding and supramolecular structures of triptycene-derived secondary dicarboxamides

The synthesis and X-ray crystal structures of triptycene-derived secondary dicarboxamides 1 and 4-7 and reference compounds 2, 3, and 8 are reported. For comparison, molecular conformations of 1-8 in the gas phase and those of 1 and 3-6 in CD2Cl2 investigated by AM1 modeling and 1H NMR spectroscopy, respectively, are also included. The solid-state conformations of 1 and 5-8 are folded and compact, resulting from the cooperative effects of intramolecular amide-amide hydrogen bonding and edge-to-face arene-arene interactions between the triptycene and the N-acetylsulfanilyl groups. The sulfonyl ester groups are also essential in the folding of 1 and 5-8 and function as structural turn units. In contrast, the conformations of 2-4 are unfolded due to the lack of one of these three essentials. The extended triptycene ring systems in 6 and 7 provide an arene-arene contact mode that is different from that for 1 and 5. While AM1 calculations suggest that the two possible arene-arene contact modes in 6 and 7 have similar conformational energies, the one observed in the solid state is also favored in solutions. To achieve a more regular shape for compact crystal packing, the bulky triptycene groups tend to pack in pairs. As a result, the intermolecular amide-amide hydrogen bonding is perturbed and modified with the participation of either the sulfonyl groups or the methanol solvent molecules, leading to various hydrogen-bonding motifs for these triptycene diamides.     

Spectroscopy and femtosecond dynamics of type-II CdTe/CdSe core-shell quantum dots.

Syntheses of CdTe/CdSe type-II quantum dots (QDs) using CdO and CdCl2 as precursors for core and shell, respectively, are reported. Characterization was made via near-IR interband emission, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDX), and X-ray diffraction (XRD). Femtosecond fluorescence upconversion measurements on the relaxation dynamics of the CdTe core (in CdTe/CdSe) emission and CdTe/CdSe interband emission reveal that as the size of the core increases from 5.3, 6.1 to 6.9 nm, the rate of photoinduced electron separation decreases from 1.96, 1.44 to 1.07 x10(12) s(-1). The finite rates of the initial charge separation are tentatively rationalized by the small electron-phonon coupling, causing weak coupling between the initial and charge-separated states.     

Experimental and theoretical investigations of rate coefficients of the reaction S(3P)+O2 in the temperature range 298-878 K

Rate coefficients of the reaction S+O(2) with Ar under 50 Torr in the temperature range 298-878 K were determined with the laser photolysis technique. S atoms were generated by photolysis of OCS with a KrF excimer laser at 248 nm; their concentration was monitored via resonance fluorescence excited by atomic emission of S produced from microwave-discharged SO(2). Our measurements show that k(298 K)=(1.92+/-0.29)x10(-12) cm(3) molecule(-1) s(-1), in satisfactory agreement with previous reports. New data determined for 505-878 K show non-Arrhenius behavior; combining our results with data reported at high temperatures, we derive an expression k(T)=(9.02+/-0.27)x10(-19)T(2.11+/-0.15) exp[(730+/-120)/T] cm(3) molecule(-1) s(-1) for 298< or =T< or =3460 K. Theoretical calculations at the G2M (RCC2) level, using geometries optimized with the B3LYP/6-311+G(3df) method, yield energies of transition states and products relative to those of the reactants. Rate coefficients predicted with multichannel RRKM calculations agree satisfactorily with experimental observations; the reaction channel via SOO(1A') dominates at T<500 K, whereas channels involving formation of SOO(3A") followed by isomerization to SO(2) before dissociation, and formation of SOO(1A") followed by direct dissociation, become important at high temperatures, accounting for the observed rapid increase in rate coefficient.