Measurements of electron-transfer rates of charge-storage molecular monolayers on Si(100). Toward hybrid molecular/semiconductor information storage devices

Redox kinetics were measured for two electroactive molecules attached to Si(100) surfaces, a ferrocene (Fc-BzOH) and a Zn(II) trimesitylporphyrin (Por-BzOH). Each molecule was derivatized with a benzyl alcohol linker for attachment to the Si surface via the formation of a Si-O bond. A complete protocol was developed for the preparation of stable Si(100) surfaces derivatized with the electroactive molecules. The redox-kinetic measurements were performed on the resulting Fc-BzOH and Por-BzOH monolayers to probe (1) the rate of electron transfer (k0) for oxidation in the presence of applied potentials and (2) the rate of charge dissipation after the applied potential is disconnected (in the form of a charge-retention half-life t1/2). The k0 values for the two types of monolayers were found to be similar to one another as were the t1/2 values. Perhaps more importantly, the electron-transfer rates for both the Fc-BzOH and the Por-BzOH monolayers differ from the charge-dissipation rates by approximately 6 orders of magnitude and are strongly dependent on the surface concentration of the electroactive species. For the Por-BzOH monolayers on Si(100), the k0 and t1/2 values and their trends as a function of surface coverage were determined to be similar to those previously measured for the analogous thiol-derivatized molecule assembled on Au(111). In contrast, the Fc-BzOH monolayers on Si(100) were found to exhibit much slower electron-transfer and charge-dissipation rates than those in the corresponding thiol-Au(111) case. Two alternative hypotheses are advanced to explain both the diminution in rates with increased surface coverage and the contrasting behavior with the analogous thiols on Au, one based on space-charge effects at the monolayer-solution interface, and a second relying on changes in distance of the redox centers from the surface as modulated by the orientation of the linking chains. Collectively, the ability to prepare and study stable, electroactive molecular media on Si(100) is likely to be key in the development of hybrid molecular/semiconductor devices.     

Scandium-catalyzed allylboration of aldehydes as a practical method for highly diastereo- and enantioselective construction of homoallylic alcohols

A general approach for the allylation of aldehydes using stable, air-tolerant camphor-based chiral allylboronates under Sc(OTf)3 catalysis is described. This practical methodology provides both syn and anti propionate units and other homoallylic alcohols with very high levels of diastereo- and enantioselectivity for several substrates, including functionalized aliphatic aldehydes useful toward the elaboration of complex natural products.     

A new approach to the synthesis of 2-vinylthiophenes and selenophenes; competition between free radical and anionic cycloaromatization of bridged di- and tetrapropargylic sulfides and selenides

A series of unknown di- and tetrapropargylic sulfides and selenides have been prepared. In the presence of t-BuOK in dry THF these compounds underwent isomerization to the corresponding diallenes, followed by a tandem anionic cyclization and aromatization to 2-vinylthiophene or selenophene derivatives. Some mechanistic studies indicated competition between free radical and anionic cycloaromatization. The latter is influenced by the nature of the bridging heteroatom, substitution of the allenyl group and base concentration.     

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.     

A study of the Immune Epitope Database for some fungi species using network topological indices

In the last years, the encryption of system structure information with different network topological indices has been a very active field of research. In the present study, we assembled for the first time a complex network using data obtained from the Immune Epitope Database for fungi species, and we then considered the general topology, the node degree distribution, and the local structure of this network. We also calculated eight node centrality measures for the observed network and compared it with three theoretical models. In view of the results obtained, we may expect that the present approach can become a valuable tool to explore the complexity of this database, as well as for the storage, manipulation, comparison, and retrieval of information contained therein.     

A novel ultrasonic strain gauge for single-sided measurement of a local 3D strain field

A novel method is introduced for the measurement of a 3D strain field by exploiting the interaction between ultrasound waves and geometrical characteristics of the insonified specimen. First, the response of obliquely incident harmonic waves to a deterministic surface roughness is utilized. Analysis of backscattered amplitudes in Bragg diffraction geometry then yields a measure for the in-plane strain field by mapping any shift in angular dependency. Secondly, the analysis of the reflection characteristics of normal incident pulsed waves in frequency domain provides a measure of the out-of-plane normal strain field component, simply by tracking any change in the stimulation condition for a thickness resonance. As such, the developed ultrasonic strain gauge yields an absolute, contactless and single-sided mapping of a local 3D strain field, in which both sample preparation and alignment procedure are needless. Results are presented for cold-rolled DC06 steel samples onto which skin passing of the work rolls is applied. The samples have been mechanically loaded, introducing plastic strain levels ranging from 2 % up to 35 %. The ultrasonically measured strains have been validated with various other strain measurement techniques, including manual micrometer, longitudinal and transverse mechanical extensometer and optical mono- and stereovision digital image correlation. Good agreement has been obtained between the ultrasonically determined strain values and the results of the conventional methods. As the ultrasonic strain gauge provides all three normal strain field components, it has been employed for the extraction of Lankford ratios at different applied longitudinal plastic strain levels, revealing a strain dependent plastic anisotropy of the investigated DC06 steel sheet.     

Reactivity of p-phenyl substituted β-Enamino compounds using K-10/ultrasound. II. Synthesis of isoxazoles and 5-Isoxazolones

The condensation of 4-phenyl substituted β-enamino ketones 1a-d and β-enamino esters 5a-d with hydroxylamine hydrochloride using K-10 as the solid support under sonication was studied to evaluate the formation of isoxazole and 5-isoxazolone rings from β-enamino compounds with a substituted aromatic ring. Isoxazoles 2a-c, 3c-d and 5-isoxazolones 6a-c and 7a-d were obtained. The use of K-10/ultrasound in this reaction furnished novel results in some cases.     

Collars and partitions of hyperbolic cone-surfaces

For compact Riemann surfaces, the collar theorem and Bers’ partition theorem are major tools for working with simple closed geodesics. The main goal of this article is to prove similar theorems for hyperbolic cone-surfaces. Hyperbolic two-dimensional orbifolds are a particular case of such surfaces. We consider all cone angles to be strictly less than π to be able to consider partitions. Emily B. Dryden—partially supported by the US National Science Foundation grant DMS-0306752. Hugo Parlier—supported by the Swiss National Science Foundation grants 21-57251.99 and 20-68181.02.