Strong polarization in the optical transmission through elliptical nanohole arrays

Strong polarization dependence is observed in the optical transmission through nanohole arrays in metals. It is shown that the degree of polarization is determined by the ellipticity and orientation of the holes; the polarization axis lies perpendicular to the broad edge of the ellipse. Furthermore, the depolarization ratio shows a squared dependence on the aspect ratio of the holes, which is discussed in terms of coupling into and out of the surface plasmon modes. The observed results will be useful for tailoring the polarization behavior of metallic nanophotonic elements in many applications, including surface plasmon enhanced optical sensing and ultrafast optical switching.     

Studies in nuclear magnetic resonance—IX. Rotational barriers in substituted N,N-dimethylbenzamides

The barriers to rotation about the C? N bond in eighteen substituted N,N-dimethylbenzamides have been determined by complete line shape analysis of the NMR spectra of the N,N-dimethyl protons. The barriers have been correlated with the substituent constants σ and σ⁺. It has been shown that polar solvents increase the barrier in N,N-dimethylbenzamide. Acid catalysis of rotation about the amide C? N bond in N-(p-N,N-dimethylcarboxamidobenzyl)-pyridinium bromide has been investigated. ¹⁸O exchange studies show that catalysis is due to N-protonation rather than the formation of a tetrahedral intermediate. The rate of rotation is a function of the Hammett acidity function, H₀, and the water activity, and it is shown that proton exchange between the N- and O-protonated species involves the intermediacy of a water molecule. The differences in chemical shifts for the non-equivalent N, N-dimethyl groups of the benzamides are also a function of the substituents. Possible explanations of this phenomenon are discussed.     

A potential application for large diameter pellicular supports in the reversed phase study of ultra high molecular mass polystyrenes

Summary Ultra high molecular mass (> 7 million dalton) polystyrenes are prone to degradation in size exclusion chromatography. In gradient elution reversed phase HPLC they do not elute visibly on small particle size porous supports. However, large diameter C18 pellicular particles were successfully employed for reversed phase study of ultra high molecular mass (15 million dalton) polystyrenes without polymer degradation during elution. Although retention for the lower molecular mass polystyrenes was lower than on small diameter porous particles, the medium high molecular mass polystyrenes (0.5–1 million dalton) showed similar retention. The addition of small diameter porous particles in small quantities, to the large diameter pellicular particles, increased the amount of retention of the low molecular mass polystyrenes without affecting the higher molecular mass polystyrenes.     

The 42Ca(α, γ)46Ti and 42Ca(α, p)45Sc cross sections and the mass-45 bottleneck

The yield of γ-rays from the reaction ⁴²Ca(α, γ)⁴⁶Ti has been measured as a function of bombarding energy over the range E_α = 3.42–5.62 MeV and from ⁴²Ca(α, pγ)⁴⁵Sc over the range E_α = 4.06–5.92 MeV, and the yield of protons from the reaction ⁴²Ca(α, p)⁴⁵Sc has been measured over the range E_α = 4.78–5.92 MeV. Cross sections for all three reactions have been extracted from the data and compared with global statistical-model calculations. The agreement is good. Thermonuclear reaction rates under stellar conditions appropriate for silicon burning are calculated and their significance for the approach to and bridging of the mass-45 bottleneck in the upward flow of nucleosynthesis is discussed.     

Positron decays of 25Al, 37K, 38K and 39Ca

Allowed β⁺ decay branches from ²⁵AI, ³⁷K, ³⁸K and ³⁹Ca have been sought by observation of delayed γ-radiation. The precision of previously known branches has been increased and improved limits obtained for unobserved branches.     

Surface plasmon sensor based on the enhanced light transmission through arrays of nanoholes in gold films

Arrays of nanoholes in a gold film were used to monitor the binding of organic and biological molecules to the metallic surface. This technique is particularly sensitive to surface binding events because it is based upon the resonant surface plasmon enhanced transmission through the array of nanoholes. The sensitivity was found to be 400 nm per refractive index unit, which is comparable to other grating-based surface plasmon resonance (SPR) devices. The array of nanoholes is well suited for dense integration in a sensor chip. Furthermore, the optical geometry is collinear, which simplifies the alignment with respect to the traditional Kretschmann (reflection) arrangement for SPR sensing.     

Reversed phase behaviour of high molar mass polystyrenes in acetonitrile with halogenated methane solvent mixtures

Summary The reversed phase behaviour of high molecular mass polystyrenes was investigated on a C18 bonded phase column using acetonitrile as the polar mobile phase component and dichloromethane, chloroform and carbon tetrachloride, as separate nonpolar components. Solvent solubility compositions, elution compositions and resolutions of the various molar mass polystyrenes were measured and compared for each of the three mobile phases. Anomalous behaviour of the polystyrenes was not observed in any of the three mobile phases and only minor differences in resolution were observed. By comparing these results with previously published work, it is suggested that any mobile phase component that is both nonpolar and a good solvent for the polymer can be combined with acetonitrile for effective separations of polystyrenes by mass and that it is the poor solvent component of the mobile phase that is responsible for the anomalous behaviour that is sometimes observed in this type of chromatography.     

Improved synthesis of 4,4′-diamino-2,2′-bipyridine from 4,4′-dinitro-2,2′-bipyridine-N,N′-dioxide

A superior synthetic route to 4,4′-diamino-2,2′-bipyridine has been developed. This procedure compares favorably with existing methods, producing 4 times the yield previously reported. In addition, mild reaction conditions are utilized, allowing a considerably more efficient production, and subsequent purification, of the diamino complex.     

Iridium-mediated isomerization-cyclization of bicyclic Pauson-Khand derived allylic alcohols

Treatment of 2-(toluene-4-sulfonyl)-2,3,4,4a,5,6-hexahydro-1H-[2]pyrindin-6-ol 10, accessed from the diastereoselective Luche reduction of a Pauson-Khand derived bicylic cyclopentenone, with a catalytic amount of (1,5-cyclooctadiene)(pyridine)(tricyclohexylphosphine)iridium(I) hexafluorophosphate 1 (Crabtree's catalyst) under a hydrogen atmosphere resulted in the formation of 4-(toluene-4-sulfonyl)-2-oxa-4-azatricyclo[5.2.1.0(3,8)]decane 12 as a single diastereoisomer. This process is likely to proceed via an initial Ir(I)-mediated isomerization of the alkene to form an N-sulfonyl enamine 11, followed by cyclization. Evidence to support this came when, after short reaction periods, 11 was isolated, characterized spectroscopically, and on resubmission to the reaction conditions formed 12.