Effects of the thickness of birefringent coatings

It is known that birefringent coatings are a powerful experimental technique for the determination of surface strains of metals or other opaque bodies. In this paper the complete state of strain in such a coating is determined for an arbitrary one-dimensional variation of the displacement at the metal surface. It is shown that strain gradients or curvature of the surface have a pronounced effect on the observed birefringence, and must be taken into consideration. This can be done by means of two correction factors derived in the paper which take into account the elastic properties of the coating and its thickness. An experimental procedure is outlined for determining an unknown distribution of strain at the metal surface on the basis of the observed photoelastic pattern.     

Fluorogel Elastomers with Tunable Transparency,Elasticity, Shape‐Memory,and Antifouling Properties

Omniphobic fluorogel elastomers were prepared by photocuring perfluorinated acrylates and a perfluoropolyether crosslinker. By tuning either the chemical composition or the temperature that control the crystallinity of the resulting polymer chains, a broad range of optical and mechanical properties of the fluorogel can be achieved. After infusing with fluorinated lubricants, the fluorogels showed excellent resistance to wetting by various liquids and anti‐biofouling behavior, while maintaining cytocompatiblity.     

A molecular orbital treatment of the basicity of oxyanion units

The basicity of the oxidic groups AlO₄^5?, SiO₄^4?, PO₄^3?, SO₄^2?, ClO₄^?, can be regarded in terms of electron donor power and expressed numerically as the optical basicity, λ. The λ value depends upon the oxidation number of the central atom and its basicity moderating parameter, γ. The results of (modified) self-consistent field CNDO calculations, presented and discussed in this paper, indicate the simple relationship that the optical basicity value is directly proportional to the negative charge borne by the oxygen atoms of the oxyanion. It is apparent that the basicity moderating parameter is a measure of the ability of the central atom to withdraw charge from the oxygen atoms. The results also indicate that the electron density at the “surface” of the oxyanion originates not only from the oxygens but also from the central atom, this effect increasing with decreasing oxidation number of the central atom.     

An empirical study of the effect of the variables in a flash vacuum pyrolysis (FVP) experiment

The effect of the variation of the experimental parameters on the conversion of precursor to products in a typical flash vacuum pyrolysis (FVP) experiment was investigated empirically. Temperature-conversion plots can be used to optimise FVP conditions and their mechanistic significance is exemplified. At a given temperature, the conversion can be increased by an increase in the background pressure, or by packing a section of the furnace tube with inert material (particularly when placed at the trap end of the furnace tube) or by employing a catalyst. Despite the prevailing view that only intramolecular reactions take place by FVP, it has been shown by a 'dual-FVP' cross-over experiment that the dimerisation of benzyl radicals occurs in the gas-phase, before the cold trap, under standard conditions. However, reduction in through-put rate, increase in furnace temperature and reduction in background pressure all reduce the amount of gas-phase coupling.     

Total synthesis of (+/-)-cameroonan-7alpha-ol and biomimetic rearrangements to related nopsane sesquiterpenes

A total synthesis of the novel silphinane sesquiterpene alcohol (+/-)-cameroonanol (6-OH) from bicyclic enone 10 was accomplished by conjugate addition of crotylsilane, photochemical hydrobromination, intramolecular alkylation, and hydride reduction. The stereoisomers cameroonan-7beta-ol (18-OH) and 9-epicamerooonanols (19 and 20) were separated from isomer mixtures and the 9-desmethylcameroonanols (21-OH and 22-OH) were obtained by similar means. Solvolysis of 6-OMs and 18-OMs effected skeletal rearrangements to (+/-)-silphiperfol-6-ene (5), (+/-)-prenopsanol (7) and (+/-)-nopsanol (8), and (+/-)-silphiperfolan-7beta-ol (9) in parallel with biogenetic schemes proposed for these naturally occurring sesquiterpenes. The nor analogues 21-OMs and 22-OMs underwent solvolytic rearrangments to a similar set of nor products. The increase in solvolytic rates for the 7beta-mesylates 18-OMs and 22-OMs in comparison to the 7alpha epimers is attributed to concerted antiperiplanar Wagner-Meerwein rearrangements to the prenopsyl and norprenopsyl carbocations. Further analysis of the kinetic data and comparisons with solvolysis rates for the structurally related silphin-1beta-yl and silphin-1alpha-yl mesylates (28 and 29) are presented. The rearrangements observed afford chemical precedent for the biogenetic pathways in the literature for these silphinane sesquiterpenes.     

Effects of ligand tuning on dinuclear indium catalysts for lactide polymerization

Functionalized diaminophenols, H(N(R1R2)N(R3)O), were investigated as ligands for indium catalysts in the ring-opening polymerization of racemic lactide. Precursor complexes (N(Me2)N(Me)O)InCl(2) (1), (N(Pr2)NO)InCl(2) (2), and (N(Mes)NO)InCl(2) (3) were synthesized and fully characterized by (1)H and (13)C NMR spectroscopy, elemental analysis, and single-crystal X-ray crystallography. Complexes 1 and 2 were used to synthesize alkoxy-bridged complexes [(N(Me2)N(Me)O)InCl](2)(μ-Cl)(μ-OEt) (4) and [(N(Pr2)NO)InCl](2)(μ-Cl)(μ-OEt) (5). These complexes catalysed the polymerization of racemic lactide at different rates, with complex 5 being substantially more active than complex 4. The dissociation behaviour of these catalysts in the presence of lactide was also studied and used to make comparisons with previously reported catalyst systems.     

Guest editor's tribute to Friedrich Baucke on the occasion of his 80th birthday

The results of experiments where Tl⁺ and Pb²⁺ ions are electrolysed into a sodium borate glass (35 mol% Na₂O and 50 °C) are brought up to date in order to take into account recent developments in the chemistry of borate glasses. It is first necessary to consider the unique chemistry of the oxide(-II) species in terms of its electronegativity, electronic polarisability and acid–base properties, and the significant relationship between these is discussed. It is described how the Lewis basicity of oxidic materials such as glasses can be expressed quantitatively on the optical basicity scale and how determinations are made by various experimental methods. These methods include optical spectroscopy of ‘probe’ ions such as Tl⁺ or Pb²⁺, measurement of electronic polarisability and far-infrared spectroscopic ‘rattling’ frequencies of constituent metal ions. When Pb²⁺ ions are electrolysed into the sodium borate glass, it is found that there is migration of Na⁺ ions away from and of O²⁻ ions towards the (lead) anode with formation of PbO. There is almost complete depletion of Na₂O in the anode region so that the composition of the glass approximates to B₂O₃. A similar process occurs to a limited degree in the case of thallium, but the Tl⁺ ions are able to penetrate more deeply into the glass. Their ultraviolet ¹S₀ → ³P₁ frequency indicates that the sites they occupy have much greater basicity than the bulk glass. The two-site model of Kamitsos proposes that in borate glasses, there are higher and lower basicity sites, and the measured optical basicity of Tl⁺ indicates occupation of the higher sites. Since it has been shown that BO₄ groups in the glass are weakly basic, it is unlikely that they are involved in the higher sites. It is discussed how the higher site basicity implies greater covalency in the interaction of the Tl⁺ ion with the oxide(-II)s that constitute the pathway, and it is suggested that this is an important factor in the electromigration process.     

LIAD-fs scheme for studies of ultrafast laser interactions with gas phase biomolecules

Laser induced acoustic desorption (LIAD) has been used for the first time to study the parent ion production and fragmentation mechanisms of a biological molecule in an intense femtosecond (fs) laser field. The photoacoustic shock wave generated in the analyte substrate (thin Ta foil) has been simulated using the hydrodynamic HYADES code, and the full LIAD process has been experimentally characterised as a function of the desorption UV-laser pulse parameters. Observed neutral plumes of densities >10(9) cm(-3) which are free from solvent or matrix contamination demonstrate the suitability and potential of the source for studying ultrafast dynamics in the gas phase using fs laser pulses. Results obtained with phenylalanine show that through manipulation of fundamental femtosecond laser parameters (such as pulse length, intensity and wavelength), energy deposition within the molecule can be controlled to allow enhancement of parent ion production or generation of characteristic fragmentation patterns. In particular by reducing the pulse length to a timescale equivalent to the fastest vibrational periods in the molecule, we demonstrate how fragmentation of the molecule can be minimised whilst maintaining a high ionisation efficiency.