Spectral design of temperature-invariant narrow bandpass filters for the mid-infrared

The ability of narrow bandpass filters to discriminate wavelengths between closely-separated gas absorption lines is crucial in many areas of infrared spectroscopy. As improvements to the sensitivity of infrared detectors enables operation in uncontrolled high-temperature environments, this imposes demands on the explicit bandpass design to provide temperature-invariant behavior. The unique negative temperature coefficient (dn/dT<0) of Lead-based (Pb) salts, in combination with dielectric materials enable bandpass filters with exclusive immunity to shifts in wavelength with temperature. This paper presents the results of an investigation into the interdependence between multilayer bandpass design and optical materials together with a review on invariance at elevated temperatures.

Thermopile radiometer signal conditioning for surface atmospheric radiation measurements

A highly stable microvolt amplifier for use with atmospheric broadband thermopile radiometers is described. The amplifier has a nominal gain of 500, for bipolar input signals in the range +/- 10 mV from a floating source. The noise level at the input is less than 5 mu V (at 100 k Omega input impedance), permitting instantaneous diffuse solar radiation measurements to 0.5 W m(-2) resolution with 12 bit analog to digital conversion. The temperature stability of gain is better than 5 ppm/degrees C (-4 to 20 degrees C). Averaged over a decade of use, the long term drift of the amplifier gain is less than similar to 0.02%/yr. As well as radiometers measuring solar and terrestrial radiations, the amplifier has also been successfully used with low level signals from thermocouples and ground heat flux plates.

Adaptation of crops to climate change through genotypic responses to mean and extreme temperatures

The importance of temperature in the determination of the yield of an annual crop (groundnut; Arachis hypogaea L. in India) was assessed. Simulations from a regional climate model (PRECIS) were used with a crop model (GLAM) to examine crop growth under simulated current (1961-1990) and future (2071-2100) climates. Two processes were examined: the response of crop duration to mean temperature and the response of seed-set to extremes of temperature. The relative importance of, and interaction between, these two processes was examined for a number of genotypic characteristics, which were represented by using different values of crop model parameters derived from experiments. The impact of mean and extreme temperatures varied geographically, and depended upon the simulated genotypic properties. High temperature stress was not a major determinant of simulated yields in the current climate, but affected the mean and variability of yield under climate change in two regions which had contrasting statistics of daily maximum temperature. Changes in mean temperature had a similar impact on mean yield to that of high temperature stress in some locations and its effects were more widespread. Where the optimal temperature for development was exceeded, the resulting increase in duration in some simulations fully mitigated the negative impacts of extreme temperatures when sufficient water was available for the extended growing period. For some simulations the reduction in mean yield between the current and future climates was as large as 70%, indicating the importance of genotypic adaptation to changes in both means and extremes of temperature under climate change. (c) 2006 Elsevier B.V. All rights reserved.

Heat tolerance in groundnut

Tolerance to high soil and air temperature during the reproductive phase is an important component of adaptation to and and semi-arid cropping environments in groundnut. Between 10 and 22 genotypes were screened for tolerance to high air and soil temperature in controlled environments. To assess tolerance to high soil temperature, 10 genotypes were grown from start of podding to harvest at ambient (28 degrees) and high (38 degreesC) soil temperatures, and crop growth rate (CGR), pod growth rate (PGR) and partitioning (ratio PGR:CGR) measured. To assess tolerance to high air temperature during two key stages-microsporogenesis (3-6 days before flowering, DBF) and flowering, fruit-set was measured in two experiments. In the first experiment, 12 genotypes were exposed to short (3-6 days) episodes of high (38 degreesC) day air temperature at 6 DBF and at flowering. In the second experiment, 22 genotypes were exposed to 40 degreesC day air temperature for I day at 6 DBF, 3 DBF or at flowering. Cellular membrane thermostability (relative injury, RI) was also measured in these 22 genotypes. There was considerable variation among genotypes in response to high temperature, whether assessed by growth rates, fruit-set or RI. Pod weight at high soil temperature was associated with variation in CGR rather than partitioning. Flowering was more sensitive to high air temperature than microsporogenesis. Genotypes tolerant to high air temperature at microsporogenesis were not necessarily tolerant at flowering, and nor was tolerance correlated with RI. Six genotypes (796, 55-437, ICG 1236, ICGV 86021, lCGV 87281 and ICGV 92121) were identified as heat tolerant based on their performance in all tests. These experiments have shown that groundnut genotypes can be easily screened for reproductive tolerance to high air and soil temperature and that several sources of heat tolerance are available in groundnut germplasm. (C) 2003 Elsevier Science B.V. All rights reserved.

Phenotyping parents of mapping populations of rice for heat tolerance during anthesis

Seed set of rice (Oryza sativa L.) is highly sensitive to short episodes of high temperature at anthesis events that are likely to be more frequent in future climates. Breeding for tolerance is therefore an essential component of adaptation to climate variability and change. Experiments were conducted in 2003 and 2004 at optimum (30 degrees C daytime) and high (35 and 38 degrees C) air temperature using parents of some prominent mapping populations (i) to determine whether there were differences in the daily flowering pattern and hence a potential heat avoidance mechanism, and (ii) to identify rice genotypes having true heat tolerance during anthesis, that is, high seed set in spikelets exposed to high temperature. Rice cultivar CG14 (O. glaberrima) reached peak anthesis earlier in the morning (1.5 h after dawn) under both control (30 degrees C) and high (38 degrees C) temperature conditions than O. sativa genotypes (>= 3 h after dawn). Exposure to high temperature (centered on the time of peak anthesis) for 6 h reduced spikelet fertility more than exposure for 2 h, and fertility was lower at 38 degrees C than at 35 degrees C. Genotypic ranking for spikelet fertility at 35 and 38 degrees C was highly correlated in both 2003 and 2004. Fertility was also highly correlated across years, suggesting a consistent and reproducible response of spikelet fertility to temperature. The check cultivar N22 was the most heat tolerant genotype (64-86% fertility at 38 degrees C) and cultivars Azucena and Moroberekan the most susceptible (<8%).

Characterisation of the thermodormancy response in the everbearing strawberry 'Everest'

Temperature regimes that induce and ameliorate cropping troughs ("thermodormancy") were evaluated over two seasons for the everbearing strawberry 'Everest'. When plants were exposed to 26 degrees C for 5, 10, 20 or 30 d in July, heat-induced troughs in cropping were observed in August. An important discovery was that cool (13 degrees C) night temperatures ameliorated the severity of thermodormancy. In this study, thermodormancy appeared to be due principally to flower abortion post-anthesis, as large numbers of flowers emerged in mid-July, during the high temperature treatments, but went on to produce low fruit numbers in mid-August. Flower initiation itself (monitored by crown dissection) was not reduced by high temperatures. The observation that night-time temperature is critical for thermodormancy has significance for commercial production, in which protected cropping tends to increase average temperatures throughout the season, and venting tends to focus on day-time temperatures.

The role of Ti3+ interstitials in TiO2(110) reduction and oxidation

Here we describe results which teach us much about the mechanism of the reduction and oxidation of TiO2(110) by the application of scanning tunnelling microscopy imaging at high temperatures. Titania reduces at high temperature by thermal oxygen loss to leave localized (i.e. Ti3+) and delocalized electrons on the lattice Ti, and a reduced titania interstitial that diffuses into the bulk of the crystal. The interstitial titania can be recalled to the surface by treatment in very low pressures of oxygen, occurring at a significant rate even at 573 K. This re-oxidation occurs by re-growth of titania layers in a Volmer-Weber manner, by a repeating sequence in which in-growth of extra titania within the cross-linked (1 x 2) structure completes the (1 x 1) bulk termination. The next layer then initiates with the nucleation of points and strings which extend to form islands of cross-linked (1 x 2), which once again grow and fill in to reform the (1 x 1). This process continues in a cyclical manner to form many new layers of well-ordered titania. The details of the mechanism and kinetics of the process are considered.

Bending, twisting, and breaking CuCN chains to produce framework materials: the reactions of CuCN with alkali-metal halides

The reactions of the low-temperature polymorph of copper(I) cyanide (LT-CuCN) with concentrated aqueous alkali-metal halide solutions have been investigated. At room temperature, KX (X = Br and I) and CsX (X = Cl, Br, and I) produce the addition products K[Cu-2(CN)(2)Br](H2O)-H-. (I), K-3[Cu-6(CN)(6)I-3](.)2H(2)O (II), Cs[Cu-3(CN)(3)Cl] (III), Cs[Cu-3(CN)(3)Br] (IV), and Cs-2[Cu-4(CN)(4)I-2](H2O)-H-. (V), with 3-D frameworks in which the -(CuCN)- chains present in CuCN persist. No reaction occurs, however, with NaX (X = Cl, Br, I) or KCl. The addition compounds, I-V, reconvert to CuCN when washed. Both low- and high-temperature polymorphs of CuCN (LT- and HT-CuCN) are produced, except in the case of Cs[Cu-3(CN)(3)Cl] (III), which converts only to LT-CuCN. Heating similar AX-CuCN reaction mixtures under hydrothermal conditions at 453 K for 1 day produces single crystals of I-V suitable for structure determination. Under these more forcing conditions, reactions also occur with NaX (X = Cl, Br, I) and KCl. NaBr and KCl cause some conversion of LT-CuCN into HT-CuCN, while NaCl and NaI, respectively, react to form the mixed-valence Cu(I)/Cu(II) compounds [Cu-II(OH2)(4)][Cu-4(I)(CN)(6)], a known phase, and [Cu-II(OH2)(4)][Cu-4(I)(CN)(4)I-2] (VI), a 3-D framework, which contains infinite -(CuCN)- chains. After 3 days of heating under hydrothermal conditions, the reaction between KI and CuCN produces [Cu-II(OH2)(4)][Cu-2(I)(CN)I-2](2) (VII), in which the CuCN chains are broken into single Cu-CN-Cu units, which in turn are linked into chains via iodine atoms and then into layers via long Cu-C and Cu-Cu interactions.

Dithioacetalisation of PEEK: a general technique for the solubilisation and characterisation of semi-crystalline aromatic polyketones

The family of semi-crystalline, aromatic, high-temperature thermoplastics known as poly(ether-ketone)s are insoluble in conventional organic solvents, but undergo completely general and quantitatively reversible reactions with alkanedithiols in strong acid media, to give soluble poly(dithioacetal)s, which are readily characterisable by GPC and light scattering techniques.

Advances in cycloaddition polymerizations

Cycloaddition reactions have been employed in polymer synthesis since the mid-nineteen sixties. This critical review will highlight recent notable advances in this field. For example, [2 + 2] cycloaddition reactions have been utilized in numerous polymerizations to enable the construction of strained polymer systems such as poly(2-azetidinone)s that can, in turn, afford polyfunctional beta-amino acid derived polymers. Polymers have also been synthesized successfully via (3 + 2) cycloaddition methods utilizing both thermal and high-pressure conditions. 'Click chemistry'-a process involving the reaction of azides with olefins, has also been adopted to generate linear and hyperbranched polymer architectures in a very efficient manner. [4 + 2] Cycloadditions have also been utilized under thermal and high-pressure conditions to produce rigid polymers such as polyimides and polyphenylenes. These cycloaddition polymerization methods afford polymers with potential for use in high performance polymers applications such as high temperature resistant coatings and polymeric organic light emitting diodes.

Ordering on multiple lengthscales in a series of side group liquid crystal block copolymers containing a cholesteryl-based mesogen

Hierarchical ordering in a side group liquid crystal block copolymer is investigated by differential scanning calorimetry, polarized optical microscopy, small-angle X-ray and neutron scattering (SAXS and SANS) and transmission electron microscopy (TEM). A series of block copolymers with a range of compositions was prepared by atom transfer radical polymerization, comprising a polystyrene block and a poly(methyl methacrylate) block bearing chiral cholesteryl mesogens. Smectic ordering is observed as well as microphase separation of the block copolymer. Lamellar structures were observed for far larger volume fractions than for coil-coil copolymers (up to a volume fraction of liquid crystal block, f(LC) = 0.8). A sample with f(LC) = 0.86 exhibited a hexagonal-packed cylinder morphology, as confirmed by SAXS and TEM. The matrix comprised the liquid crystal block, with the mesogens forming smectic layers. For the liquid crystal homopolymer and samples with high f(LC), a smectic-smectic phase transition was observed below the clearing point. At low temperature, the smectic phase comprises coexisting domains with monolayer S-A,S-1 coexisting with interdigitated S-A,S-d domains. At high temperature a SA,1 phase is observed. This is the only structure observed for samples with lower f(LC). These unprecedented results point to the influence of block copolymer microphase separation on the smectic ordering.

Thermo-responsive poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) block copolymers synthesized by RAFT polymerization: micellization and gelation

RAFT polymerization was used to prepare PMMA-b-PNIPAM copolymers. Two different chain transfer agents, tBDB and MCPDB, were used to mediate the sequential polymerizations. Micellar solutions and gels were prepared from the resulting copolymers in aqueous solution. When heated above T-c of PNIPAM (about 31 degrees C), DLS revealed that PNIPAM coronas collapsed, resulting in aggregation of the original micelles. The micellar gels underwent syneresis above T-c as water was expelled from the ordered gel structure, the lattice periodicity of which was determined by SANS. A large decrease in lattice spacing was observed above T-c. The gel became more viscoelastic at high temperature, as revealed by shear rheometry which showed a large increase in G".

Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.

Reducing acrylamide precursors in raw materials derived from wheat and potato

A review of agronomic and genetic approaches as strategies for the mitigation of acrylamide risk in wheat and potato is presented. Acrylamide is formed through the Maillard reaction during high-temperature cooking, such as frying, roasting, or baking, and the main precursors are free asparagine and reducing sugars. In wheat flour, acrylamide formation is determined by asparagine levels and asparagine accumulation increases dramatically in response to sulfur deprivation and, to a much lesser extent, with nitrogen feeding. In potatoes, in which sugar concentrations are much lower, the relationships between acrylamide and its precursors are more complex. Much attention has been focused on reducing the levels of sugars in potatoes as a means of reducing acrylamide risk. However, the level of asparagine as a proportion of the total free amino acid pool has been shown to be a key parameter, indicating that when sugar levels are limiting, competition between asparagine and the other amino acids for participation in the Maillard reaction determines acrylamide formation. Genetic approaches to reducing acrylamide risk include the identification of cultivars; and other germplasm in which free asparagine and/or sugar levels are low and the manipulation of genes involved in sugar and amino acid metabolism and signaling. These approaches are made more difficult by genotype/ environment interactions that can result in a genotype being "good" in one environment but "poor" in another. Another important consideration is the effect that any change could have on flavor in the cooked product. Nevertheless, as both wheat and potato are regarded as of relatively high acrylamide risk compared with, for example, maize and rice, it is essential that changes are achieved that mitigate the problem.

Cyclam derivatives containing three acetate pendant arms: synthesis, acid-base, metal complexation and structural studies

The ligands 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic-11-methylphosphonic acid (H(5)te3a1p) and 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic acid (H(3)te3a) were synthesized, the former one for the first time. The syntheses of these ligands were achieved from reactions on 1,4,8,11-tetraazacyclotetradecane-1,4,8-tris( carbamoylmethyl) hydroiodide (te3am center dot HI), and compounds (Hte3am)(+), 1, and (H(7)te3a1p)(2+), 4, were characterized by X-ray diffraction. Structures of two other compounds resulting from side-reactions, (H(2)te2lac)(2+), 2, and (H(4)te2a2p(OEt2))(2+), 3, were also determined by X-ray diffraction. Potentiometric titrations of H(5)te3a1p and H(3)te3a were performed at 298.2 K and ionic strength 0.10 mol dm(-3) in NMe4NO3 to determine their protonation constants. H-1 and P-31 NMR titrations of H(5)te3a1p were carried out in order to determine the very high first protonation constant of this ligand and to elucidate the sequence of protonation. Potentiometric studies of the two ligands with Ca2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ metal ions performed in the same experimental conditions showed that the complexes of H5te3a1p present very high thermodynamic stability while complexes of H(3)te3a, particularly Co2+ and Zn2+, are even more stable. P-31 NMR spectra of the cadmium(II) complex of H(5)te3a1p showed that the phosphonate moiety was coordinated to the metal ion. The UV-vis-NIR spectroscopic data and magnetic moment values of Co2+ and Ni2+ complexes of H(5)te3a1p and H(3)te3a together with the EPR of the corresponding Cu2+ complexes indicated that all these complexes adopt distorted octahedral coordination geometries in solution. This was confirmed by the single crystal structure of [Cu-2(Hte3a)(H2O)(3)Cl]Cl-0.5(ClO4)(0.5) center dot 2H(2)O that showed two distorted octahedral copper centres bridged by a N-acetate pendant arm with a Cu center dot center dot center dot Cu distance of 4.890(1) angstrom. The first one is encapsulated into the macrocyclic cavity surrounded by four nitrogen and two oxygen donors from the macrocycle, whereas the second one is on the periphery of the macrocycle and is coordinated to two oxygen atoms of one acetate pendant arm in chelating fashion, one chloride and three water molecules.