Kinetics and dynamics measured using IntraCavity Laser Absorption Spectroscopy

IntraCavity Laser Absorption Spectroscopy (ICLAS) is a high-resolution, high sensitivity spectroscopic method capable of measuring line positions, linewidths, lineshapes, and absolute line intensities with a sensitivity that far exceeds that of a traditional multiple pass absorption cell or Fourier Transform spectrometer. From the fundamental knowledge obtained through these measurements, information about the underlying spectroscopy, dynamics, and kinetics of the species interrogated can be derived. The construction of an ICLA Spectrometer will be detailed, and the measurements utilizing ICLAS will be discussed, as well as the theory of operation and modifications of the experimental apparatus. Results include: i) Line intensities and collision-broadening coefficients of the A band of oxygen and previously unobserved, high J, rotational transitions of the A band, hot-band transitions, and transitions of isotopically substituted species. ii) High-resolution (0.013 cm-1) spectra of the second overtone of the OH stretch of trans-nitrous acid recorded between 10,230 and 10,350 cm-1. The spectra were analyzed to yield a complete set of rotational parameters and an absolute band intensity, and two groups of anharmonic perturbations were observed and analyzed. These findings are discussed in the context of the contribution of overtone-mediated processes to OH radical production in the lower atmosphere.

AQA A2 Unit 4 Chemistry : kinetics, equilibria and organic chemistry.

Guía de apoyo para alumnos de educación secundaria de segundo ciclo que sigan la especificación de AQA (Assessment and Qualifications Alliance) en el nivel A2 del área de química. Está dividida en tres secciones: una introducción con consejos y técnicas para la realización del examen; una guía de contenido con los principales conceptos y temas (cinética, equilibrio, ácidos y bases, nomenclatura e isomería en química orgánica, compuestos del grupo carbonilo, química aromática, aminas, aminoácidos, polímeros, análisis y síntesis orgánica y determinación de estructura); y una sección con preguntas de examen y respuestas comentadas por un examinador.

Pressure-jump-induced kinetics reveals a hydration dependent folding/unfolding mechanism of ribonuclease A

Pressure-jump (p-jump)-induced relaxation kinetics was used to explore the energy landscape of protein folding/unfolding of Y115W, a fluorescent variant of ribonuclease A. Pressure-jumps of 40MPa amplitude (5ms dead-time) were conducted both to higher (unfolding) and to lower (folding) pressure, in the range from 100 to 500MPa, between 30 and 50°C. Significant deviations from the expected symmetrical protein relaxation kinetics were observed. Whereas downward p-jumps resulted always in single exponential kinetics, the kinetics induced by upward p-jumps were biphasic in the low pressure range and monophasic at higher pressures. The relative amplitude of the slow phase decreased as a function of both pressure and temperature. At 50°C, only the fast phase remained. These results can be interpreted within the framework of a two-dimensional energy surface containing a pressure- and temperature-dependent barrier between two unfolded states differing in the isomeric state of the Asn-113–Pro-114 bond. Analysis of the activation volume of the fast kinetic phase revealed a temperature-dependent shift of the unfolding transition state to a larger volume. The observed compensation of this effect by glycerol offers an explanation for its protein stabilizing effect

The effect of thermal conductivity of RIM moulds in kinetics cure

Reaction Injection Moulding (RIM) is a moulding technology used for the production of large size and complex plastic parts. The RIM process is characterized essentially by the injection of a highly reactive chemical system (usually polyurethane) and fast cure, in a mould properly closed and thermally controlled. Several studies show that rapid manufacturing moulds obtained in epoxy resins for Thermoplastic Injection Moulding (TIM) affect the moulding process and the final properties of parts. The cycle time and mechanical properties of final parts are reduced, due to a low thermal conductivity of epoxy materials. In contrast, the low conductivity of materials usually applied for the rapid manufacturing of RIM moulds, increase the mechanical properties of final injected parts and reduce the cycle time. This study shows the effect of the rapid manufacturing moulds material during the RIM process. Several materials have been tested for rapid manufacturing of RIM moulds and the analysis of both, temperature profile of moulded parts during injection and the cure data experimentally obtained in a mixing and reaction cell, allow to determine and model the real effect of the mould material on the RIM process.

Exploring the enzymatic landscape: distribution and kinetics of hydrolytic enzymes in soil particle-size fractions

The location of extracellular enzymes within the soil architecture and their association with the various soil components affects their catalytic potential. A soil fractionation study was carried out to investigate: (a) the distribution of a range of hydrolytic enzymes involved in C, N and P transformations, (b) the effect of the location on their respective kinetics, (c) the effect of long-term N fertilizer management on enzyme distribution and kinetic parameters. Soil (silty clay loam) from grassland which had received 0 or 200 kg N ha(-1) yr(-1) was fractionated, and four particle-size fractions (> 200, 200-63, 63-2 and 0. 1-2 mum) were obtained by a combination of wet-sieving and centrifugation, after low-energy ultrasonication. All fractions were assayed for four carbohydrases (beta-cellobiohydrolase, N-acetyl-beta-glucosammidase, beta-glucosidase and beta-xylosidase), acid phosphatase and leucine-aminopeptidase using a microplate fluorimetric assay based on MUB-substrates. Enzyme kinetics (V-max and K-m) were estimated in three particle-size fractions and the unfractionated soil. The results showed that not all particle-size fractions were equally enzymatically active and that the distribution of enzymes between fractions depended on the enzyme. Carbohydrases predominated in the coarser fractions while phosphatase and leucine-aminopeptidase were predominant in the clay-size fraction. The Michaelis constant (K.) varied among fractions, indicating that the association of the same enzyme with different particle-size fractions affected its substrate affinity. The same values of Km were found in the same fractions from the soil under two contrasting fertilizer management regimes, indicating that the Michaelis constant was unaffected by soil changes caused by N fertilizer management. (C) 2004 Elsevier Ltd. All rights reserved.

Uptake kinetics of metals by the earthworm Eisenia fetida exposed to field-contaminated soils

It is well known that earthworms can accumulate metals. However, most accumulation studies focus on Cd-, Cu-, Pb- or Zn-amended soils, additionally few studies consider accumulation kinetics. Here we model the accumulation kinetics of 18 elements by Eisenia fetida, exposed to 8 metal-contaminated and 2 uncontaminated soils. Tissue metal concentration was determined after 3, 7,14, 21, 28 and 42 days. Metal elimination rate was important in determining time to reach steady-state tissue metal concentration. Uptake flux to elimination rate ratios showed less variation and lower values for essential than for non-essential metals. In theory kinetic rate constants are dependent only on species and metal. Therefore it should be possible to predict steady-state tissue metal concentrations on the basis of very few measurements using the rate constants. However, our experiments show that it is difficult to extrapolate the accumulation kinetic constants derived using one soil to another. (C) 2009 Elsevier Ltd. All rights reserved.

Atmospheric chemistry of C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH: temperature dependence of the kinetics of their reactions with OH radicals, atmospheric lifetimes and global warming potentials

The atmospheric chemistry of several gases used in industrial applications, C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH, has been studied. The discharge flow technique coupled with mass-spectrometric detection has been used to study the kinetics of their reactions with OH radicals as a function of temperature. The infrared spectra of the compounds have also been measured. The following Arrhenius expressions for the reactions were determined (in units of cm3 molecule-1 s-1): k(OH + HFE-7200) = (6.9+2.3-1.7) × 10-11 exp(-(2030 ± 190)/T); k(OH + HFE-7100) = (2.8+3.2-1.5) × 10-11 exp(-(2200 ± 490)/T); k(OH + HFE-7000) = (2.0+1.2-0.7) × 10-11 exp(-(2130 ± 290)/T); and k(OH + C3F7CH2OH) = (1.4+0.3-0.2) × 10-11 exp(-(1460 ± 120)/T). From the infrared spectra, radiative forcing efficiencies were determined and compared with earlier estimates in the literature. These were combined with the kinetic data to estimate 100-year time horizon global warming potentials relative to CO2 of 69, 337, 499 and 36 for HFE-7200, HFE-7100, HFE-7000 and CF3CF2CF2CH2OH, respectively.

Introducing improved cultivars: Understanding farmers' seed drying and storage practices in central Ghana

Improved upland rice cultivars introduced in Volta Region, Ghana, have been perceived to store poorly compared to farmers' traditional cultivars. A survey was conducted in 2003 in the Hohoc district of this region, where a participatory Varietal Selection programme had started in 1997, to gain insight into fanners' seed production and storage practices that are likely to affect seed quality in storage. Farmers rated keeping quality (p < 0.001), tolerance to storage pests (p < 0.001), seed quality (p < 0.001) and establishment of their local cultivars Kawomo, Viono and Wuwulili as much better than the improved cultivar IDSA 85. Initial seed moisture content ranged from 12.8 to 18% and germination from 0 to 82%. There was a significant relationship between seed moisture content and duration of drying prior to storage (p < 0.001) and storage method (p = 0.015). Germination loss in storage was rapid at high moisture content and slow at low moisture content. Between 60 and 80% of seeds germinated after six Months storage at 12.8% moisture content. The viability equation predicted accurately germination of farmer-saved seed stored under ambient temperature in Ghana. Except for the japonica rice cultivar WAB 126-18-HB, the traditional cultivars Kawomo, Viono and Wuwulili survived better in storage than improved cultivars. There is a need to improve seed quality of improved cultivars if farmers are to benefit from their higher yields and grain quality and to improve storage practices.

Priming and re-drying improve the survival of mature seeds of Digitalis purpurea during storage

Most priming studies have been conducted on commercial seed lots of unspecified uniformity and maturity, and subsequent seed longevity has been reported to both increase and decrease. Here a seed lot of Digitalis purpurea L. with relatively uniform maturity and known history was used to analyse the effects of priming on seed longevity in air-dry storage. Seeds collected close to natural dispersal and dried at 15 % relative humidity (RH), 15 degrees C, were placed into experimental storage (60 % RH, 45 degrees C) for 14 or 28 d, primed for 48 h at 0, -1, -2, -5, -10 or -15 MPa, re-equilibrated (47 % RH, 20 degrees C) and then returned to storage. Further seed samples were primed for 2 or 48 h at -1 MPa and either dried at 15 % RH, 15 degrees C or immediately re-equilibrated for experimental storage. Finally, some seeds were given up to three cycles of experimental storage and priming (48 h at -1 MPa). Priming at -1 MPa had a variable effect on subsequent survival during experimental storage. The shortest lived seeds in the control population showed slightly increased life spans; the longer lived seeds showed reduced life spans. In contrast, seeds first stored for 14 or 28 d before priming had substantially increased life spans. The increase tended to be greatest in the shortest lived fraction of the seed population. Both the period of rehydration and the subsequent drying conditions had significant effects on longevity. Interrupting air-dry storage with additional cycles of priming also increased longevity. The extent of prior deterioration and the post-priming desiccation environment affect the benefits of priming to the subsequent survival of mature seeds. Rehydration-dehydration treatments may have potential as an adjunct or alternative to the regeneration of seed accessions maintained in gene banks for plant biodiversity conservation or plant breeding.

Effects of restricted water availability and increased temperature on the grain filling, drying and quality of winter wheat

Experiments in controlled environments examined the effects of the timing and severity of drought, and increased temperature, on grain development of Hereward winter wheat. Environmental effects on grain specific weight, protein content, Hagberg Falling Number, SDS-sedimentation volume, and sulphur content were also studied. Drought and increased temperature applied before the end of grain filling shortened the grain filling period and reduced grain yield, mean grain weight and specific weight. Grain filling was most severely affected by drought between days 1-14 after anthesis. Protein content was increased by stresses before the end of grain growth, because nitrogen harvest index was less severely affected than was dry matter harvest index. Hagberg Falling Number was increased to the greatest extent by stresses applied 15-28 days after anthesis. Treatment effects on grain sulphur content were similar to those on protein content, such that N:S ratio was not significantly affected by drought nor temperature stresses. The effects of restricted water on grain yield and quality were linearly related to soil moisture between 44 and about 73% field capacity (FC) from days 15-28. Drought stress (but not temperature stress) before the end of grain filling decreased SDS-sedimentation volume relative to drought applied later. (C) 2003 Elsevier Science Ltd. All rights reserved.

Drying method influences the development of germinability, dessication tolerance and subsequent longevity of immature seeds of sumauma (Ceiba pentandra (L.) Gaertn. [Bombacaceae])

The ability to germinate, tolerate desiccation and survive in air-dry storage was investigated during early seed development in planta and subsequent ex planta maturation of sumauma (Ceiba pentandra). Immature fruits were collected on three different dates (i.e. from about 5 days before until 7 days after mass maturity). Immature fresh seeds were not able to germinate. Fruits or seeds were subjected immediately after each collection to three different drying treatments with progressively slower rates of dessication: (i) seeds were extracted from the fruits and dried immediately; (ii) fruits were dried in a thin layer; (iii) fruits were dried in a tied polyethylene bag (with 10 holes of 1cm diameter). Drying was in a room maintained at 25 degrees C +/- 3 degrees C and 65%+/- 5% r.h. For treatment (i) the seeds were dried for 6 days in order to reduce moisture content to around 13% ( +/- 2%) moisture content. For treatments (ii) and (iii) the fruits were subjected to different periods of drying depending upon collection date. The results of these post-collection treatments showed generally that the more immature the seeds the slower the rate of drying that is required to improve ability to germinate, ability to tolerate desiccation and potential longevity, but at the third harvest, 7 days after mass maturity, the intermediate drying rate treatment was the most beneficial. Thus post fruit collection treatments can be modified depending upon the stage of seed development in order to provide good to high quality seeds of sumauma when collection has to be made at a site with difficult access at less than ideal times. The results are relevant to seed collection practices for both forestry and ex situ plant biodiversity conservation.

Effects of volatile fatty acid supply on their absorption and on water kinetics in the rumen of sheep sustained by intragastric infusions

Three sheep fitted with a ruminal cannula and an abomasal catheter were used to study water kinetics and absorption of VFA infused continuously into the rumen. The effects of changing VFA concentrations in the rumen by shifting VFA infusion rates were investigated in an experiment with a 3 x 3 Latin square design. On experimental days, the animals received the basal infusion rate of VFA (271 mmol/h) during the first 2 h. Each animal then received VFA at a different rate (135, 394, or 511 mmol/h) for the next 7.5 h. Using soluble markers (polyethylene glycol and Cr-EDTA), ruminal volume, liquid outflow, apparent water absorption, and VFA absorption rates were estimated. There were no significant effects of VFA infusion rate on ruminal volume and water kinetics. As the VFA infusion rate was increased, VFA concentration and osmolality in the rumen were increased and pH was decreased. There was a biphasic response of liquid outflow to changes in the total VFA concentration in the rumen, as both variables increased together up to a total VFA concentration of 80.1 mM, whereas, beyond that concentration, liquid outflow remained stable at an average rate of 407 mL/h. There were significant linear (P = 0.003) and quadratic (P = 0.001) effects of VFA infusion rate on the VFA absorption rate, confirming that VFA absorption in the rumen is mainly a concentration-dependent process. The proportion of total VFA supplied that was absorbed in the rumen was 0.845 (0.822, 0.877, and 0.910 for acetate, propionate, and butyrate, respectively). The molar proportions of acetate, propionate, and butyrate absorbed were affected by the level of VFA infusion in the rumen, indicating that this level affected to a different extent the absorption of the different acids.

Near infrared reflectance spectroscopy (NIRS) to predict biological parameters of maize silage: effects of particle comminution, oven drying temperature and the presence of residual moisture

Maize silage nutritive quality is routinely determined by near infrared reflectance spectroscopy (NIRS). However, little is known about the impact of sample preparation on the accuracy of the calibration to predict biological traits. A sample population of 48 maize silages representing a wide range of physiological maturities was used in a study to determine the impact of different sample preparation procedures (i.e., drying regimes; the presence or absence of residual moisture; the degree of particle comminution) on resultant NIR prediction statistics. All silages were scanned using a total of 12 combinations of sample pre-treatments. Each sample preparation combination was subjected to three multivariate regression techniques to give a total of 36 predictions per biological trait. Increased sample preparations procedure, relative to scanning the unprocessed whole plant (WP) material, always resulted in a numerical minimisation of model statistics. However, the ability of each of the treatments to significantly minimise the model statistics differed. Particle comminution was the most important factor, oven-drying regime was intermediate, and residual moisture presence was the least important. Models to predict various biological parameters of maize silage will be improved if material is subjected to a high degree of particle comminution (i.e., having been passed through a 1 mm screen) and developed on plant material previously dried at 60 degrees C. The extra effort in terms of time and cost required to remove sample residual moisture cannot be justified. (c) 2005 Elsevier B.V. All rights reserved.