Impurity effects at hydrophobic surfaces

The effective charge of hydrophobic surfaces and in particular of the air–water interface is a crucial parameter for electrochemistry, colloidal chemistry and interfacial science, but different experiments give conflicting estimates. Zeta-potential and disjoining-pressure measurements point to a strongly negative surface charge, often interpreted as being due to adsorbing hydroxide ions. In contrast, surface tension measurements of acids and bases suggest the hydronium ion to be surface active, in agreement with some surface-specific non-linear spectroscopy results. The air–electrolyte interfacial tension exhibits a characteristic minimum at millimolar electrolyte concentration for all salts, the so-called Jones–Ray effect, which points to competitive adsorption mechanisms present in dilute electrolyte solutions. We show that all these puzzling experimental findings can be explained by the presence of trace amounts of surface-active charged impurities, most likely anionic surfactants.     

Stereospecific polymerization of o-methoxystyrene by anionic initiators

o-Methoxystyrene was polymerized with n-butyllithium (n-BuLi), Na naphthalene, and K dispersion as initiators in tetrahydrofuran (THF) and toluene. The stereoregularity of the polymer was investigated by means of the NMR spectroscopy. The methoxy resonance of the spectrum split into ten components due to the tactic pentads. It was found by x-ray examination that the polymer obtained by n-BuLi in toluene at ?45°C was crystalline and highly isotactic. In THF, the stereospecificity of the polymerization was independent of the initiator, and the isotacticity of the polymer increased with increasing reaction temperature. In toluene, the stereospecificity depended on the initiator; i.e., n-BuLi gave a polymer with higher isotacticity than that given by phenylsodium. The fraction of isotactic triad of the polymer obtained by n-BuLi in toluene at ?78°C was more than 90%, but 50% at 50°C. The presence of ca. 1% THF in toluene led to a steep decrease in the isotacticity even at ?78°C. The tacticity of the polymer given by Na naphthalene was not affected by the existence of NaB(C₆H₅)₄ in THF. The polymerization in THF could be explained by Bovey's “single σ” process, while a penultimate effect was observed in the polymerization by n-BuLi in toluene.     

Enhanced electron-capture decay rate of 7Be encapsulated in C60 cages

The decay rate of 7Be electron capture was measured in C60 and Be metal with a reference method. The half-life of 7Be endohedral C60 ((7)Be@C(60)) and 7Be in Be metal (Be metal (7Be)) is found to be 52.68+/-0.05 and 53.12+/-0.05 days, respectively. This amounts to a 0.83% difference in electron-capture decay half-life between (7)Be@C(60) and Be metal (7Be). Our result is a reflection of the different electron wave functions for (7)Be@C(60) inside C60 compared to the situation when 7Be is in a Be metal.     

STM observation of surface phases of Sn/Cu(0 0 1)

Geometrical structures of the Sn-adsorbed Cu(0 0 1) surfaces are studied with scanning tunneling microscopy. There are four phases in the Sn coverage range between 0.2 and 0.5 mono-atomic layer (ML). On the basis of the observed atomic images in this range, we propose structural models for the phases with 0.33 and 0.375 ML of Sn. All the phases consist of embedded Sn atoms in the Cu surface, forming two-dimensional surface alloy structures. On the surface with ∼0.4 ML of Sn, a novel one-dimensional structure is observed.     

Anionic copolymerization of 1,1-diphenylethylene and 2,3-dimethylbutadiene

1,1-Diphenylethylene (M₂) and 2,3-dimethylbutadiene (M₁) were copolymerized with n-butyllithium in tetrahydrofuran. The rate of consumption of each monomer was followed by the change of high resolution NMR spectra of the reaction mixture. The copolymerization proceeded alternately, if the ratio of initial monomer concentrations, [M₂]₀/[M₁]₀, was sufficiently larger than unity. By assuming the rate constant k₂₂ to be zero, the constants k₂₁ were obtained from the consumption rates of the monomers. In the alternating copolymerization, 2,3-dimethylbutadiene was incorporated into the copolymer only as the 1,4-structure, while the 1,2-structure was predominant in homopolymerization.     

Influence of the carbon nanotube probe tilt angle on the effective probe stiffness and image quality in tapping-mode atomic force microscopy

Previous studies have shown that when using carbon nanotubes (CNTs) as tapping-mode AFM probes, their tilt angle with respect to vertical (denoted phi) must be close to 0 degrees to obtain high-quality images and that very poor images are obtained for phi > 30 degrees . Here we present a quantitative theoretical investigation of the effect of phi on tapping-mode AFM imaging for single-wall and multiwall nanotube (SWNT and MWNT, respectively) probes of diameters 3.4-5.5 nm and aspect ratio 7.5, which have been found ideal for imaging via TEM. Using molecular and classical dynamics, we investigate the effect of phi on CNT probe stiffness (quantified through the maximum gradient of the tip-sample interaction force) and show that it decreases linearly with increasing phi, becoming negligible at around phi approximately 40 degrees , thus confirming the conclusions of previous studies. We find that MWNT probe stiffness is proportional to the number of walls, but that the difference in stiffness between SWNTs and MWNTs also decreases linearly with increasing phi and becomes negligible at around phi approximately 40 degrees . The simulated cross-sectional scans of a sample SWNT using two different values of phi show that the image can be distorted and shifted laterally when phi is large, in some cases giving measured heights appreciably greater than the sample dimensions. We show analytically that the tip-sample forces that occur during imaging can be significantly lower when CNT probes are used instead of conventional probes, even in the absence of buckling, and that they can be further reduced by increasing phi. On the basis of this result, we propose the design of free-standing kinked probes for the characterization of sensitive samples, whereby the probe approaches the sample at a vertical orientation and possesses a tilted section that regulates the tip-sample interaction forces.     

Centrifugal concentrator for the substitution of nitrogen blow-down micro-concentration in dioxin/polychlorinated biphenyl sample preparation

A centrifugal concentrator was applied for the substitution of nitrogen blow-down micro-concentration in dioxin/PCB sample preparation. Automation was achieved through this apparatus and resulted in significant improvements in sample preparation productivity, along with excellent reproducibility and recovery rate of dioxin/PCB. Mean recoveries of dioxin congeners were 90-106%, respectively.     

Electron addition spectrum in the supersymmetric t-J model with inverse-square interaction

The electron addition spectrum A+(k,omega) is obtained analytically for the one-dimensional (1D) supersymmetric t-J model with 1/r2 interaction. The result is obtained first for a small-sized system and its validity is checked against the numerical calculation. Then the general expression is found which is valid for arbitrary size of the system. The thermodynamic limit of A+(k,omega) has a simple analytic form with contributions from one spinon, one holon, and one antiholon-all of which obey fractional statistics. The upper edge of A+(k,omega) in the (k,omega) plane includes a delta-function peak which reduces to that of the single-electron band in the low-density limit.     

Design Method for Ultrabroadband Optical Parametric Chirped Pulse Amplification

Multiple amplification stages with different phase-matching angles were designed to yield stable and ultrabroadband amplification in optical parametric chirped pulse amplification by optimally controlling the idler laser pulses. Numerical results showed that the overall temporal duration of the amplified seed laser pulse and subsequently the spectral bandwidth can be amplified by using multiple amplification stages in comparison with those of the initial seed pulse laser, which is suitable to generate a high-energy pulse with ultrashort pulse duration in a simple manner.