Estimating Hydrogen Cyanide in Forage Sorghum (Sorghum bicolor) by Near-Infrared Spectroscopy

Hydrogen cyanide (HCN) is a toxic chemical that can potentially cause mild to severe reactions in animals when grazing forage sorghum. Developing technologies to monitor the level of HCN in the growing crop would benefit graziers, so that they can move cattle into paddocks with acceptable levels of HCN. In this study, we developed near-infrared spectroscopy (MRS) calibrations to estimate HCN in forage sorghum and hay. The full spectral NIRS range (400-2498 nm) was used as well as specific spectral ranges within the full spectral range, i.e., visible (400-750 nm), shortwave (800-1100 nm) and near-infrared (NIR) (1100-2498 nm). Using the full spectrum approach and partial least-squares (PLS), the calibration produced a coefficient of determination (R-2) = 0.838 and standard error of cross-validation (SECV) = 0.040%, while the validation set had a R-2 = 0.824 with a low standard error of prediction (SEP = 0.047%). When using a multiple linear regression (MLR) approach, the best model (NIR spectra) produced a R-2 = 0.847 and standard error of calibration (SEC) = 0.050% and a R-2 = 0.829 and SEP = 0.057% for the validation set. The MLR models built from these spectral regions all used nine wavelengths. Two specific wavelengths 2034 and 2458 nm were of interest, with the former associated with C=O carbonyl stretch and the latter associated with C-N-C stretching. The most accurate PLS and MLR models produced a ratio of standard error of prediction to standard deviation of 3.4 and 3.0, respectively, suggesting that the calibrations could be used for screening breeding material. The results indicated that it should be feasible to develop calibrations using PLS or MLR models for a number of users, including breeding programs to screen for genotypes with low HCN, as well as graziers to monitor crop status to help with grazing efficiency.

Dendritic structures produced on solidification of multicomponent aqueous solutions

Dendrite structures of ice produced on undirectional solidification of ternary and quaternary aqueous solutions have been studied. Upon freezing, solutions containing more than one solute produce plate-shaped dendrites of ice. The spacing between dendrites increase linearly with the distance from the chill surface and the square root of local solidification time (or square root of inverse freezing rate) for any fixed composition. For fixed freezing conditions, the dendrite spacings from multicomponent aqueous solutions were a function of the concentrations and diffusion coefficients of the individual solutes. The dendrite spacing produced by freezing of a solution was changed by the addition of a solute different from those already present. If the main diffusion coefficient of the added solute is higher than that of solutes already present, the dendrite spacing is increased and vice versa. The dendrite spacing in multi-component systems increases with the total solute concentration if the constituent solutes are present in equal amounts. The dendrite spacing obtained on freezing of these dilute multicomponent solutions can be expressed by regression equations of the type Image Full-size image (2K) where L is the dendrite spacing in microns, C1, C2 and C3 are concentrations of individual solutes, Θf is the total freezing time and A1 −A8 are constants. A Yates analysis of the dendrite spacings in a factorial design of quaternary solutions indicates that there are strong interactions between individual solutes in regard to their effect on the dendrite spacings. A mass transport analysis has been used to calculate the interdendritic supersaturation ΔC of the individual solutes, the supercooling in the interdendritic liquid ΔT, and the transverse growth velocity of the dendrites, VT. In ternary solutions if two solutes are present in equal amount the supersaturation of the solute with higher main diffusion coefficient is lower, and vice versa. If a solute with higher main diffusion coefficient is added to a binary solution, the interface growth velocity, the interdendritic supersaturation of the base solute and the interdendritic supercooling increase with the quantity of solute added.

Pressure dependence of 35Cl nuclear quadrupole resonance in 2,5-, 2,6- and 3,5-dichlorophenols

Pressure dependence of the 35Cl Nuclear Quadrupole Resonances (N.Q.R.) in 2,5-, 2,6- and 3,5-dichlorophenols (DCP) has been studied up to a pressure of about 6·5 kbar at room temperature. While the pressure dependence of the two resonance lines in 2,6-DCP is essentially similar, the lower frequency line in 2,5-DCP is almost pressure independent and the higher frequency line shows a linear variation with pressure upto about 3·5 kbar but shows a negative pressure coefficient beyond this pressure. The two lines in 3,5-DCP have a non-linear pressure dependence with the curvature changing smoothly with pressure. The pressure coefficient for both lines becomes negative beyond a pressure of 5 kbar. The pressure dependence of the N.Q.R. frequencies is discussed in relation to intra- and inter-molecular contacts. Also, a thermodynamic analysis of the data is carried out to determine the constant volume temperature derivative of the N.Q.R. frequency.

Sorghum dwarfing genes can affect radiation capture and radiation use efficiency

Presence of the dw3 sorghum dwarfing gene had negative effects on grain yield in some genetic backgrounds and environments. In a previous study we showed that this was due to a significant reduction in shoot biomass (mainly via reduced stem mass), which in turn negatively affected grain size. The current study examines whether shoot biomass was reduced via effects of dw3 on traits associated with resource capture, such as leaf area index (LAI), light interception (LI), and canopy extinction coefficient (k) or with resource use efficiency, such as radiation use efficiency (RUE). Three pairs of near-isogenic sorghum lines differing only in the presence or absence of the dwarfing allele dw3 (3-dwarfs vs 2-dwarfs) were grown in large field plots. Biomass accumulation and LI were measured for individual canopy layers to examine canopy characteristics of tall and short types. Similar to the previously reported effects on grain yield, the effects of dw3 on RUE, LI and k varied among genetic backgrounds and environments. Interactions between dw3 and genetic background, but also interactions with environment are likely to have modulated the extent to which RUE, LI, or k contributed to biomass differences between tall and short sorghum. © 2013 .

Reliability and validity of objective measures of physical activity in youth with cerebral palsy who are ambulatory

BACKGROUND Physical therapy for youth with cerebral palsy (CP) who are ambulatory includes interventions to increase functional mobility and participation in physical activity (PA). Thus, reliable and valid measures are needed to document PA in youth with CP. OBJECTIVE The purpose of this study was to evaluate the inter-instrument reliability and concurrent validity of 3 accelerometer-based motion sensors with indirect calorimetry as the criterion for measuring PA intensity in youth with CP. METHODS Fifty-seven youth with CP (mean age=12.5 years, SD=3.3; 51% female; 49.1% with spastic hemiplegia) participated. Inclusion criteria were: aged 6 to 20 years, ambulatory, Gross Motor Function Classification System (GMFCS) levels I through III, able to follow directions, and able to complete the full PA protocol. Protocol activities included standardized activity trials with increasing PA intensity (resting, writing, household chores, active video games, and walking at 3 self-selected speeds), as measured by weight-relative oxygen uptake (in mL/kg/min). During each trial, participants wore bilateral accelerometers on the upper arms, waist/hip, and ankle and a portable indirect calorimeter. Intraclass coefficient correlations (ICCs) were calculated to evaluate inter-instrument reliability (left-to-right accelerometer placement). Spearman correlations were used to examine concurrent validity between accelerometer output (activity and step counts) and indirect calorimetry. Friedman analyses of variance with post hoc pair-wise analyses were conducted to examine the validity of accelerometers to discriminate PA intensity across activity trials. RESULTS All accelerometers exhibited excellent inter-instrument reliability (ICC=.94-.99) and good concurrent validity (rho=.70-.85). All accelerometers discriminated PA intensity across most activity trials. LIMITATIONS This PA protocol consisted of controlled activity trials. CONCLUSIONS Accelerometers provide valid and reliable measures of PA intensity among youth with CP.

Physical activity and health related quality of life

Background Research on the relationship between Health Related Quality of Life (HRQoL) and physical activity (PA), to date, have rarely investigated how this relationship differ across objective and subjective measures of PA. The aim of this paper is to explore the relationship between HRQoL and PA, and examine how this relationship differs across objective and subjective measures of PA, within the context of a large representative national survey from England. Methods Using a sample of 5,537 adults (40–60 years) from a representative national survey in England (Health Survey for England 2008), Tobit regressions with upper censoring was employed to model the association between HRQoL and objective, and subjective measures of PA controlling for potential confounders. We tested the robustness of this relationship across specific types of PA. HRQoL was assessed using the summary measure of health state utility value derived from the EuroQol-5 Dimensions (EQ-5D) whilst PA was assessed via subjective measure (questionnaire) and objective measure (accelerometer- actigraph model GT1M). The actigraph was worn (at the waist) for 7 days (during waking hours) by a randomly selected sub-sample of the HSE 2008 respondents (4,507 adults – 16 plus years), with a valid day constituting 10 hours. Analysis was conducted in 2010. Results Findings suggest that higher levels of PA are associated with better HRQoL (regression coefficient: 0.026 to 0.072). This relationship is consistent across different measures and types of PA although differences in the magnitude of HRQoL benefit associated with objective and subjective (regression coefficient: 0.047) measures of PA are noticeable, with the former measure being associated with a relatively better HRQoL (regression coefficient: 0.072). Conclusion Higher levels of PA are associated with better HRQoL. Using an objective measure of PA compared with subjective shows a relatively better HRQoL.

The validity of the GENEActiv wrist-worn accelerometer for measuring adult sedentary time in free living

OBJECTIVES Based on self-reported measures, sedentary time has been associated with chronic disease and mortality. This study examined the validity of the wrist-worn GENEactiv accelerometer for measuring sedentary time (i.e. sitting and lying) by posture classification, during waking hours in free living adults. DESIGN Fifty-seven participants (age=18-55 years 52% male) were recruited using convenience sampling from a large metropolitan Australian university. METHODS Participants wore a GENEActiv accelerometer on their non-dominant wrist and an activPAL device attached to their right thigh for 24-h (00:00 to 23:59:59). Pearson's Correlation Coefficient was used to examine the convergent validity of the GENEActiv and the activPAL for estimating total sedentary time during waking hours. Agreement was illustrated using Bland and Altman plots, and intra-individual agreement for posture was assessed with the Kappa statistic. RESULTS Estimates of average total sedentary time over 24-h were 623 (SD 103) min/day from the GENEActiv, and 626 (SD 123) min/day from the activPAL, with an Intraclass Correlation Coefficient of 0.80 (95% confidence intervals 0.68-0.88). Bland and Altman plots showed slight underestimation of mean total sedentary time for GENEActiv relative to activPAL (mean difference: -3.44min/day), with moderate limits of agreement (-144 to 137min/day). Mean Kappa for posture was 0.53 (SD 0.12), indicating moderate agreement for this sample at the individual level. CONCLUSIONS The estimation of sedentary time by posture classification of the wrist-worn GENEActiv accelerometer was comparable to the activPAL. The GENEActiv may provide an alternative, easy to wear device based measure for descriptive estimates of sedentary time in population samples

Informational efficiency of the European Union emission allowance market

This thesis studies the informational efficiency of the European Union emission allowance (EUA) market. In an efficient market, the market price is unpredictable and profits above average are impossible in the long run. The main research problem is does the EUA price follow a random walk. The method is an econometric analysis of the price series, which includes an autocorrelation coefficient test and a variance ratio test. The results reveal that the price series is autocorrelated and therefore a nonrandom walk. In order to find out the extent of predictability, the price series is modelled with an autoregressive model. The conclusion is that the EUA price is autocorrelated only to a small degree and that the predictability cannot be used to make extra profits. The EUA market is therefore considered informationally efficient, although the price series does not fulfill the requirements of a random walk. A market review supports the conclusion, but it is clear that the maturing of the market is still in process.

Sparking potentials and swarm coefficients in Freon and mixtures of Freon and air

The sparking potentials and swarm coefficients ( ionization and attachment coefficients) were measured in Freon and Freon-air mixtures over the range of 24·3 times 10-16≤ E/ N ≤ 303 times 10-16 V cm2. Addition of Freon increased the sparking potential, and the rate of increase of the attachment coefficient with increasing percentage of Froon in the mixture was much larger than the rate of change of the first ionization coefficient.

Use of Multiblade Coordinates for Helicopter Flap-Lag Stability with Dynamic Inflow

Rotor flap-lag stability in forward flight is studied with and without dynamic inflow feedback via a multiblade coordinate transformation (MCT). The algebra of MCT is found to be so involved that it requires checking the final equations by independent means. Accordingly, an assessment of three derivation methods is given. Numerical results are presented for three- and four-bladed rotors up to an advance ratio of 0.5. While the constant-coefficient approximation under trimmed conditions is satisfactory for low-frequency modes, it is not satisfactory for high-frequency modes or for untrimmed conditions. The advantages of multiblade coordinates are pronounced when the blades are coupled by dynamic inflow.

Ultrafast Switching Time and Third Order Nonlinear Coefficients of Microwave Treated Single Walled Carbon Nanotube Suspensions

Microwave treated water soluble and amide functionalized single walled carbon nanotubes have been investigated using femtosecond degenerate pump-probe and nonlinear transmission experiments. The time resolved differential transmission using 75 femtosecond pulse with the central wavelength of 790 nm shows a bi-exponential ultrafast photo-bleaching with time constants of 160 fs (130 fs) and 920 fs (300 fs) for water soluble (amide functionalized) nanotubes. Open and closed aperture z-scans show saturation absorption and positive (negative) nonlinear refraction for water soluble (amide functionalized) nanotubes. Two photon absorption coefficient, beta(0) similar to 250 cm/GW (650 cm/GW) and nonlinear index, gamma similar to 15 cm(2)/pW (-30 cm(2)/pW) are obtained from the theoretical fit in the saturation limit to the data for two types of nanotubes.

Design of laterally loaded piles in clays based on cone penetration test data: a reliability-based approach

The behaviour of laterally loaded piles is considerably influenced by the uncertainties in soil properties. Hence probabilistic models for assessment of allowable lateral load are necessary. Cone penetration test (CPT) data are often used to determine soil strength parameters, whereby the allowable lateral load of the pile is computed. In the present study, the maximum lateral displacement and moment of the pile are obtained based on the coefficient of subgrade reaction approach, considering the nonlinear soil behaviour in undrained clay. The coefficient of subgrade reaction is related to the undrained shear strength of soil, which can be obtained from CPT data. The soil medium is modelled as a one-dimensional random field along the depth, and it is described by the standard deviation and scale of fluctuation of the undrained shear strength of soil. Inherent soil variability, measurement uncertainty and transformation uncertainty are taken into consideration. The statistics of maximum lateral deflection and moment are obtained using the first-order, second-moment technique. Hasofer-Lind reliability indices for component and system failure criteria, based on the allowable lateral displacement and moment capacity of the pile section, are evaluated. The geotechnical database from the Konaseema site in India is used as a case example. It is shown that the reliability-based design approach for pile foundations, considering the spatial variability of soil, permits a rational choice of allowable lateral loads.

Molecular Interactions Chlorin Assemblies and NMR Separations

Photosynthesis is a chemical process in which the energy of the light quanta is transformed into chemical energy. Chlorophyll (Chl) molecules play a key role in photosynthesis; they function in the antennae systems and in the photosynthetic reaction center where the primary charge separation (CS) takes place. Bio-inspired mimicry of the CS is an essential unit in dye-sensitized solar cells. Aim of this study was to design and develop electron donor-acceptor (EDA) pairs from Chls and fullerenes (C60) or carbon nanotubes (CNT). The supramolecular approach was chosen, as long synthetic sequences required by the covalent approach lead to long reaction schemes and low yields. Here, a π-interaction between soluble CNTs and Chl was used in EDA construction. Also, a beta-face selective two-point bound Chl-C60 EDA was introduced. In addition, the photophysical properties of the supramolecular EDA dyads were analyzed. In organic chemistry, nuclear magnetic resonance (NMR) spectroscopy is the most vital analytical technique in use. Multi-dimensional NMR experiments have enabled a structural analysis of complex natural products and proteins. However, in mixture analysis NMR is still facing difficulties. In many cases overlapping signals can t be resolved even with the help of multi-dimensional experiments. In this work, an NMR tool based on simple host-guest chemistry between analytes and macromolecules was developed. Diffusion ordered NMR spectroscopy (DOSY) measures the mobilities of compounds in an NMR sample. In a liquid state NMR sample, each of the analytes has a characteristic diffusion coefficient, which is proportional to the size of the analyte. With normal DOSY experiment, provided that the diffusion coefficients of the analytes differ enough, individual spectra of analytes can be extracted. When similar sized analytes differ chemically, an additive can be introduced into the sample. Since macromolecules in a liquid state NMR sample can be considered practically stationary, even faint supramolecular interaction can change the diffusion coefficient of the analyte sufficiently for a successful resolution in DOSY. In this thesis, polyvinylpyrrolidone and polyethyleneglycol enhanced DOSY NMR techniques, which enable mixture analysis of similar in size but chemically differing natural products, are introduced.

Activated carbon + HFC 134a based two stage thermal compression adsorption refrigeration using low grade thermal energy sources

A thermodynamic analysis is presented for the two stage thermal compression process for an adsorption refrigeration cycle with HFC-134a as the working fluid and activated carbon as the adsorbent. Three specimens of varying achievable packing densities were evaluated. The influence of evaporating, condensing/adsorption and desorption temperatures was assessed through three performance indicators, namely,the uptake efficiency, the coefficient of performance and the exergetic efficiency. Conditions under which a two stage thermal compression process performs better than the single stage unit are identified. It is concluded that two stage thermal compression will be a viable proposition when the heat source temperature is low or when adsorption characteristics are weak or when adequate packing densities are difficult to realize. (C) 2008 Elsevier Ltd. All rights reserved.

On various types of decoupling for time-varying system

This paper deals with the problem of decoupling a class of linear time-varying multi-variable systems, based on the defining property that the impulse response matrix of a decoupled system is diagonal. Depending on the properties of the coefficient matrices of the vector differential equation of the open-loop system, the system may be uniformly or totally decoupled. The necessary and sufficient conditions that permit a system to be uniformly or totally decoupled by state variable feedback are given. The main contribution of this paper is the precise definition of these two classes of decoupling and a rigorous derivation of the necessary and sufficient conditions which show the necessity of requiring that the system be of constant ordered rank with respect to observability. A simple example illustrates the importance of having several definitions of decoupling. Finally, the results are specialized to the case of time invariant systems.