Analytical potentials for triatomic molecules IX. The prediction of anharmonic force constants from potential energy surfaces based on harmonic force fields and dissociation energies for SO2 and O3

Analytical potential energy functions which are valid at all dissociation limits have been derived for the ground states of SO2 and O3. The procedure involves minimizing the errors between the observed vibrational spectra and spectra calculated by a variational procedure. Good agreement is obtained between the observed and calculated spectra for both molecules. Comparisons are made between anharmonic force fields, previously determined from the spectral data, and the force fields obtained by differentiating the derived analytical functions at the equilibrium configurations.

Apparent digestibility and nitrogen utilization of diets based on maize silage harvested at three stages of maturity and fed to steers

Advancing maize crop maturity is associated with changes in ear-to-stover ratio which may have consequences for the digestibility of the ensiled crop. The apparent digestibility and nitrogen retention of three diets (Early, Mid and Late) containing maize silages made from maize of advancing harvest date [dry matter (DM) contents of the maize silages were 273, 314 and 367 g kg(-1) for the silages in the Early, Mid and Late diets respectively], together with a protein supplement offered in sufficient quantities to make the diets isonitrogenous, were measured in six Holstein-Friesian steers in an incomplete Latin square design with four periods. Dry-matter intake of maize silage tended to be least for the Early diet and greatest for the Medium diet (P=0(.)182). Apparent digestibility of DM and organic matter did not differ between diets. Apparent digestibility of energy was lowest in the Late diet (P = 0(.)057) and the metabolizable energy concentrations of the three silages were calculated as 11(.)0, 11(.)1 and 10(.)6 MJ kg(-1) DM for the Early, Medium and Late diets respectively (P = 0(.)068). No differences were detected between diets in starch digestibility but the number of undamaged grains present in the faeces of animals fed the Late diet was significantly higher than with the Early and Mid diets (P = 0(.)006). The apparent digestibility of neutral-detergent fibre of the diets reduced significantly as silage DM content increased (P = 0(.)012) with a similar trend for the apparent digestibility of acid-detergent fibre (P = 0(.)078). Apparent digestibility of nitrogen (N) was similar for the Early and Mid diets, both being greater than the Late diet (P = 0(.)035). Nitrogen retention did not differ between diets. It was concluded that delaying harvest until the DM content is above 300 g kg(-1) can negatively affect the nutritive value of maize silage in the UK.

Apparent digestibility and nitrogen utilisation of diets based on maize and grass silage fed to beef steers

Substituting grass silage with maize silage in forage mixtures may result in one forage influencing the nutritive value of another in terms of whole tract nutrient digestibility and N utilisation. This experiment investigated effects of four forage combinations being, grass silage (G); 67 g/100 g grass silage + 33 g/100 g maize silage (GGM); 67 g/100 g maize silage + 33 g/100 g grass silage (MMG); maize silage (M). All diets were formulated to be isonitrogenous (22.4 g N/kg dry matter [DM]) using a concentrate mixture. Ration digestibility and N balance was determined using 7 Holstein Friesian steers (mean body weight 411.0 +/- 120.9 kg) in a cross-over design. Inclusion of maize silage in the diet had a positive linear effect on forage and total DM intake (P = 0.001), and on apparent DM and organic matter digestibility (both P = 0.048). Regardless of the silage ratio used, the metabolisable energy concentration of maize silage was calculated to be higher than that of grass silage (P = 0.058), and linearly related to the relative proportions of the two silages in the forage mixture. Inclusion of maize silage in the diet resulted in a linear decline in the apparent digestibility of starch (P = 0.022), neutral detergent fibre (P < 0.001) and acid detergent fibre (P = 0.003). Nitrogen retention, expressed as amount retained per day or in terms of body weight (g/100 kg) increased linearly with maize inclusion (P = 0.047 and 0.046, respectively). Replacing grass silage with maize silage caused linear responses according to the proportions of each forage in the diet, and that there were no associative effects of combining forages. (C) 2004 Elsevier B.V. All rights reserved.

Low-molecular-weight gelators: Elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model

This paper highlights the key role played by solubility in influencing gelation and demonstrates that many facets of the gelation process depend on this vital parameter. In particular, we relate thermal stability (T-gel) and minimum gelation concentration (MGC) values of small-molecule gelation in terms of the solubility and cooperative self-assembly of gelator building blocks. By employing a van't Hoff analysis of solubility data, determined from simple NMR measurements, we are able to generate T-calc values that reflect the calculated temperature for complete solubilization of the networked gelator. The concentration dependence of T-calc allows the previously difficult to rationalize "plateau-region" thermal stability values to be elucidated in terms of gelator molecular design. This is demonstrated for a family of four gelators with lysine units attached to each end of an aliphatic diamine, with different peripheral groups (Z or Bee) in different locations on the periphery of the molecule. By tuning the peripheral protecting groups of the gelators, the solubility of the system is modified, which in turn controls the saturation point of the system and hence controls the concentration at which network formation takes place. We report that the critical concentration (C-crit) of gelator incorporated into the solid-phase sample-spanning network within the gel is invariant of gelator structural design. However, because some systems have higher solubilities, they are less effective gelators and require the application of higher total concentrations to achieve gelation, hence shedding light on the role of the MGC parameter in gelation. Furthermore, gelator structural design also modulates the level of cooperative self-assembly through solubility effects, as determined by applying a cooperative binding model to NMR data. Finally, the effect of gelator chemical design on the spatial organization of the networked gelator was probed by small-angle neutron and X-ray scattering (SANS/SAXS) on the native gel, and a tentative self-assembly model was proposed.

Sparse kernel density estimator using orthogonal regression based on D-optimality experimental design

A novel sparse kernel density estimator is derived based on a regression approach, which selects a very small subset of significant kernels by means of the D-optimality experimental design criterion using an orthogonal forward selection procedure. The weights of the resulting sparse kernel model are calculated using the multiplicative nonnegative quadratic programming algorithm. The proposed method is computationally attractive, in comparison with many existing kernel density estimation algorithms. Our numerical results also show that the proposed method compares favourably with other existing methods, in terms of both test accuracy and model sparsity, for constructing kernel density estimates.

A stress relaxation model for the viscoelastic solids based on the steady-state creep equation

Creep and stress relaxation are inherent mechanical behaviors of viscoelastic materials. It is considered that both are different performances of one identical physical phenomenon. The relationship between the decay stress and time during stress relaxation has been derived from the power law equation of the steady-state creep. The model was used to analyse the stress relaxation curves of various different viscoelastic materials (such as pure polycrystalline ice, polymers, foods, bones, metal, animal tissues, etc.). The calculated results using the theoretical model agree with the experimental data very well. Here we show that the new mathematical formula is not only simple but its parameters have the clear physical meanings. It is suitable to materials with a very broad scope and has a strong predictive ability.