Intra‐strain Variability in the Effects of Temperature on UV‐B Sensitivity of Cyanobacteria

Stratospheric ozone depletion is mostly marked over the Antarctic and to a lesser extent over the Arctic, though recent reports have revealed that this also occurs at lower latitudes. Continued depletion of ozone in the lower stratosphere allows more UVR to reach the Earth's surface. Furthermore, it is projected that surface water temperatures will increase by between 0.2 and 2.0°C by the year 2060 and this will directly or indirectly influence algal growth. The interactions between environmental factors are complicated by the existence of different strains (ecotypes) of the same species that may respond differently. To understand the interactive effects of temperature and UV‐B on two strains of Anabaena circinalis, we investigated the damaging effects of UV‐B on cell numbers and photosynthetic characteristics and also examined the effect of temperature on the capacity of cells to recover from such stress. Both strains of A. circinalis responded differently in terms of survival, photosynthetic characteristics and recovery with interactions between temperature and UV‐B. This could be due to the variations in strain‐specific photoreactive mechanisms. This needs to be explored further including more strains and species before definitive conclusions can be reached about effects of global change on cyanobacteria generally.     

Catalytic enantioselective indium-mediated allylation of hydrazones

[reaction: see text] A facile and highly selective indium-mediated allylation of hydrazones utilizing BINOL ligands is described. Chiral (R)-3,3'-bistrifluoromethylBINOL afforded homoallylic amines in up to 97% ee with stoichiometric ligand. Employing only 10 mol % ligand afforded selectivity of up to 92% ee.     

Analysis of ochres from Clearwell Caves: the role of particle size in determining colour

Three ochre samples (A (orange-red in colour), B (red) and C (purple)) from Clearwell Caves, (Gloucestershire, UK) have been examined using an integrated analytical methodology based on the techniques of IR and diffuse reflectance UV-visible-NIR spectroscopy, X-ray diffraction, elemental analysis by ICP-AES and particle size analysis. It is shown that the chromophore in each case is haematite. The differences in colour may be accounted for by (i) different mineralogical and chemical composition in the case of the orange ochre, where higher levels of dolomite and copper are seen and (ii) an unusual particle size distribution in the case of the purple ochre. When the purple ochre was ground to give the same particle size distribution as the red ochre then the colours of the two samples became indistinguishable. An analysis has now been completed of a range of ochre samples with colours from yellow to purple from the important site of Clearwell Caves.     

Effect of varying counterions on the sensitivity of electrohydrodynamic and fast atom bombardment mass spectrometry

The abundance of ion pairs (CA⁺) relative to that of doubly charged ions (C²⁺) in electrohydrodynamic (EH) mass spectra of a series of anions with a common dication in glycerol was found to increase in the order acetate < nitrite < chloride < bromide ≈ nitrate < iodide < perchlorate. Correlation with enthalpies of hydration for the anions suggests that this trend reflects the solution chemistry of ion association. These spectra also reveal that solvation rather than interactions with the extracting field is more important in determining the overall EH mass spectrometric sensitivity to doubly charged ions. Therefore, the use of anions that promote more extensive ion pairing enhances the overall sensitivity to multiply charged ions that otherwise interact strongly with the solvent, but reduces sensitivity to singly charged ions. These observations hold in fast atom bombardment mass spectrometry, surviving the invasive effects of the primary beam.     

Oligomeric cadmium-phthalocyanine complexes: novel supramolecular free radical structures

Certain cadmium-metallated phthalocyanines give rise to EPR active triple-decker sandwich complexes containing two Cd ions and three phthalocyanine (Pc) ligands. These have been shown to form when the ligands bear either eight non- peripheral alkyl or alkenyl substituents or eight peripheral 2-ethylhexyl groups. They can be derived either from three equivalents of a cadmium phthalocyanine precursor or from a 2:1 mixture of a cadmium phthalocyanine (CdPc) and a metal-free phthalocyanine (H(2)Pc). The mode of their formation has been investigated by a series of "cross" experiments. The results indicate that the triple-decker structures are formed by a self-assembly process. This is deduced from results that show that they can disassemble and reassemble with incorporation of differently substituted ligands derived from either an H(2)Pc or CdPc. The reassembled structures in these cross experiments can contain more than one ligand that originated from either the added CdPc or, and more surprisingly, the H(2)Pc compound. Mass spectrometry has also established that higher order oligomers can be formed when steric requirements between the alkyl substituents on adjacent rings in the stack are reduced. Thus an isotopic cluster for a Cd(5)Pc(6) complex has been observed when the eight peripheral substituents are hexyl chains and tetrameric complexes are formed when two different ligands are incorporated within a stack, with one carrying substituents at the peripheral sites and the other bearing substituents at the non-peripheral sites.     

Fundamental Methods for the Phase Transfer of Nanoparticles

The utilization of nanoparticles for a variety of applications has raised much interest in recent years as new knowledge has emerged in nanochemistry. New and diverse methods for synthesis, characterization, and application of these particles have been discovered with differing degrees of ease and reproducibility. Post-synthetic modification of nanoparticles is often a required step to facilitate their use in applications. The reaction conditions and chemical environment for the nanoparticle synthesis may not support or may conflict with further reactions. For this reason, it is beneficial to have phase transfer methods for nanoparticles to allow for their dispersion in a variety of solvents. Phase transfer methods are often limited in the types and sizes of particles that can be effectively dispersed in an immiscible solvent. Currently, general transfer methods for a wide variety of nanoparticles have not been identified. New routes for phase transfer allow for utilization of a larger range of particles in applications which were previously limited by solubility and reactivity issues. In this work, we will describe the fundamental methods for the phase transfer of metallic nanoparticles. We will look at the major problems and pitfalls of these methods. The applications of phase transfer will also be reviewed, mainly focusing on catalysis and drug delivery.     

Context-dependent performance standards in DEA

Data envelopment analysis (DEA) is a mathematical approach to measuring the relative efficiency of peer decision making units (DMUs). It is particularly useful where no a priori information on the tradeoffs or relations among various performance measures is available. However, it is very desirable if “evaluation standards,” when they can be established, be incorporated into DEA performance evaluation. This is especially important when service operations are under investigation, because service standards are generally difficult to establish. The approaches that have been developed to incorporate evaluation standards into DEA, as reported in the literature, have tended to be rather indirect, focusing primarily on the multipliers in DEA models. This paper introduces a new way of building performance standards directly into the DEA structure when context-dependent activity matrixes exist for different classes of DMUs. For example, two sets of branches, whose transaction times are known to be different from each other, usually have two different activity matrixes. We develop a procedure so that a set of standard DMUs can be generated and incorporated directly into the DEA analysis. The proposed approach is applied to a sample of 100 branches of a major Canadian bank where different sets of time standards exist for three distinct groups of branches.