Oxidation of alkylsilane-based monolayers on gold

The oxidation of alkylsilane monolayers on Au has been studied by X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, contact-angle measurements, and scanning tunneling microscopy. Exposure of the monolayers at 298 K to pure O(2) or H(2)O (>5 x 10(-5) Torr and >150 000 L) does not cause oxidation. Ambient atmosphere only causes oxidation if direct sight lines are maintained to the sample. Ozone exposure results in rapid monolayer oxidation. Oxidation initially occurs only at the Si atom, resulting in formation of a cross-linked siloxane monolayer that retains alkyl surface termination. Prolonged ozone exposures result in the oxidation and subsequent loss of the alkyl chain.     

Charged particle multiplicity distributions at 200 and 900 GeV c.m. energy

Multiplicity distributions of charged particles produced in non single-diffractive collisions between protons and antiprotons at centre of mass energies of 200 and 900 GeV are presented. The data were recorded in the UA5 streamer chambers at the CERN Collider, which was operated in a pulsed mode between the two energies. A new method to correct for acceptance limitations and inefficiencies based on the principle of maximum entropy has been used. Multiplicity distributions in full phase space and in intervals of pseudorapidity are presented in tabular form. The violation of KNO scaling in full phase space found by the UA5 group at an energy of 546 GeV is confirmed also at 200 and 900 GeV. The shape of the 900 GeV distribution in full phase space is narrower in the peak region than at 200 GeV but exhibits a pronounced high multiplicity tail. The negative binomial distribution fits data at 200 GeV in all pseudorapidity intervals and in small intervals at 900 GeV. In large intervals at 900 GeV, however, the negative binomial distribution. Fits to the partially coherent laser distribution are also presented as well as comparisons with predictions of the Dual Parton, the Fritiof and the Pythia models.     

Crystal structures of crown ethers containing an alkyl diarylphosphinate or a diarylphosphinic acid unit

This paper describes the structures of pseudo-18-crown-6 compounds (2, R,R-4 and 5) in the crystals together with theoretical calculations of the electronic circular dichroism (ECD) spectra. The achiral macrocyclic phosphinic acid 5 forms hydrogen-bonded dimers in the crystal. The O1–O2 distance (2.489 Ǻ) indicates strong H-bondings. The conformations of the macrorings of the achiral phosphinate 2 and the monomers of the achiral phosphinic acid 5 are chiral. A comparison of the torsion angles of the achiral methyl phosphinate 2 and the monomeric units of achiral 5 indicates a similar geometry. The torsion angles of the chiral methyl phosphinate (R,R)-4 differ more significantly from those in achiral methyl phosphinate 2. A negative ¹B_b exciton couplet was observed in the ECD spectrum of monomeric (R,R)-6 in MeOH and H₂O as in the spectra of (R,R)-4 in all solvents. To support the idea that (R,R)-4 has basically the same conformation in the crystal and in solution, the ECD spectrum of (R,R)-4 was calculated using the geometry of the molecule in the crystal. The calculated ECD spectrum shows a reasonable agreement with the ECD spectra obtained in solution. This shows that the steric structure observed in the crystal is predominant in solution as well.     

Calibration of PM-355 nuclear track detectors; comparison of track diameter diagrams with track depth characteristics

The calibration diagrams, i.e. track diameters and track depths versus ion energy and etching time, as obtained for PM-355 track detector irradiated with He-ions are presented. The both detector characteristics are compared. The track etch rate is determined by two methods, as a function of the etch pit depth and the ion energy loss.     

Triphilic Ionic‐Liquid Mixtures: Fluorinated and Non‐fluorinated Aprotic Ionic‐Liquid Mixtures

We present here the possibility of forming triphilic mixtures from alkyl‐ and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains—polar and nonpolar—three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self‐associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long‐range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment.     

Amorphous Silicon: New Insights into an Old Material

Amorphous silicon is synthesized by treating the tetrahalosilanes SiX₄ (X=Cl, F) with molten sodium in high boiling polar and non‐polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine‐containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO?H versus the Me?OH bond either yields H‐ and/or methyl‐substituted methoxy functional silanes. Moreover, compounds, such as Me_nSi(OMe)_4?n (n=0–3) are simply accessible in more than 75 % yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes Me_nSi(OMe)_4?n in excellent (n=0:100 %) to acceptable yields (n=1:51 %; n=2:27 %); the yield of HSi(OMe)₃ is about 85 %. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon‐based products.