The influence of hyperpolarisability and field-gradient polarisability on field adsorption binding energies for He on W(111)

The effects of imaging-gas hyperpolarisability and field-gradient polarisabuity terms on field-adsorption binding energies have been explored. At best image fields for the noble imaging gases and molecular hydrogen, the correction to long-range binding energy is at most a few percent and may be neglected. At the tungsten evaporation field the correction is significant in the cases of Ar, Kr, H₂, and especially Xe. The system He on W(111) has been used as a paradigm in the investigation of short-range binding energy. The largest correction here is due to one of the field-gradient polarisabuity terms. In the field range of most relevance to the field-ion techniques the total correction is about 15–20%, and should not be neglected in detailed treatments.     

Further applications of endocyclic enamine-enone annulations : The total syntheses of rac-Sceletium alkaloid A4 and 3'-demethoxy sceletium alkaloid A4

The total synthesis of rac-sceletium alkaloid A₄1a and of its 3'-demethoxy analogue 1b via the annulation of endocyclic enamines 4a–b is presented. The Michael acceptor 5a is a useful synthon for the two-step synthesis of 2,3-disubstituted pyridines from Δ²-pyrrolines.     

Quantitative analysis of solid mixtures by diffuse reflectance measurements

The factors affecting the reflectance of an absorbing substance mixed with material not absorbing at the wavelength of measurement were investigated and it was found that the effect of particle size could be eliminated by prolonged grinding. It is shown that the percentage by weight of the absorbing substance is directly proportional to the quantity (A/R)^1.383 (R = percentage reflectance ; A = 100 — R) and that this quantity is additive for 2 absorbing substances. A method is developed for the accurate determination of low concentrations of one and two absorbing substances mixed with non-absorbing material. The method is applicable to poorly crystallized substances which give no characteristic X-ray powder diffraction patterns as well as to crystalline solids. The reflectance of some substances is shown to be dependent on the previous history of the particular sample. The method is not applicable if there is physical interaction between the components of the mixture.     

Characterization of the Reaction of Chloroacetaldehyde with Single and Double Stranded DNA

Chloroacetaldehyde reacts with viral M13mp18 single and double stranded DNA to form the highly fluorescent adducts, etheno-AMP and etheno-CMP.

Absorbance and fluorescence spectroscopy can be used to monitor and characterize these reactions. Both single and double stranded DNA showed increases in the absorbance following reaction with the aldehyde. The fluorescence also increased in these two groups and continued to rise with increasing time of incubation until a point of saturation was reached. The fluorescence of the double stranded moiety was considerably enhanced following reaction with the aldehyde while that of the single stranded population was not, making this method appropriate for the separation of small quantities of the two populations of DNA.     

Intra-cavity generation of superpositions of Laguerre–Gaussian beams

In this paper we demonstrate experimentally the intra-cavity generation of a coherent superposition of Laguerre–Gaussian modes of zero radial order but opposite azimuthal order. The superposition is created with a simple intra-cavity stop that creates equal losses for the two azimuthal modes, and we show that by adjustment of the stop we can produce modes up to azimuthal order 8. The fact that we have a coherent superposition rather than an incoherent superposition is verified by intensity measurements, propagation measurements and a decomposition of the field by an inner product executed on a phase-only spatial light modulator. Such fields have relevance in quantum information and optical trapping.     

An electron spin resonance study of dimeric,trimeric, and tetrameric paramagnetic silver atom clusters

The low temperature γ-irradiation of frozen benzene solutions containing AgClO₄ leads directly to the formation of the paramagnetic species Ag₂ ⁺, no Ag⁰ centre being detected. When benzene or toluene solutions containing AgBF₄ were similarly treated and the matrix carefully annealed, well-resolved E.S.R. spectra attributed to paramagnetic clusters containing three and four equivalent silver atoms were detected. The lack of resolved anisotropy in the spectrum of the trimer and tetramer are thought to argue in favour of a triangular and tetrahedral geometry respectively rather than linear chains.     

Twist-Bend Nematic Glasses: The Synthesis and Characterisation of Pyrene-based Nonsymmetric Dimers

A selection of pyrene-based liquid crystal dimers have been prepared, containing either methylene-ether or diether linked spacers of varying length and parity. All the diether linked materials, CBOnO.Py (n=5, 6, 11, 12), exhibit conventional nematic and smectic A phases, with the exception of CBO11O.Py which is exclusively nematic. The methylene-ether linked dimer, CBnO.Py, with an even-membered spacer (n=5) was solely nematogenic, but odd-members (n=6, 8, 10) exhibited both nematic and twist-bend nematic phases. Replacement of the cyanobiphenyl fragment by cyanoterphenyl giving CT6O.Py, gave elevated melting and nematic-isotropic transition temperatures, and SmA and SmC_A phases were observed on cooling the nematic phase. Intermolecular face-to-face associations of the pyrene moieties drive glass formation, and all these materials have a glass transition temperature at or above room temperature. The stability of the glassy twist-bend nematic phase allowed for its study using AFM, and the helical pitch length, P_TB, was measured as 6.3 and 6.7 nm for CB6O.Py and CB8O.Py, respectively. These values are comparable to the shortest pitch of a twist-bend nematic phase measured to date.