Synthesis and vibrational spectroscopic characterisation of nickel containing aurichalcite

Raman spectroscopy complimented with supplementary infrared spectroscopy has been used to characterise a synthetic nickel substituted aurichalcite a zinc/nickel hydroxy carbonate, (Zn²⁺, Cu²⁺, Ni²⁺)₅(CO₃)₂(OH)₆. XRD patterns show high orientation and indicate the presence of some minor impurities. The diffraction patterns for the Ni-aurichalcite are well correlated with the standard reference patterns. EDAX analyses indicate variations in chemical composition of Zn/Ni ratios of ∼20:1. The symmetry of the carbonate anion in aurichalcite is C_s and is composition dependent. This symmetry reduction results in multiple bands in both the symmetric stretching and bending regions. The intense band for the Ni-aurichalcite at 1070 cm⁻¹ is assigned to the ν₁(CO₃)²⁻ symmetric stretching mode. Three Raman bands assigned to the ν₃(CO₃)²⁻ antisymmetric stretching modes are observed for Ni-aurichalcite at 1372, 1480 and 1543 cm⁻¹. Multiple Raman bands are observed in the regions from 800 to 850 cm⁻¹ and 720 to 750 cm⁻¹, and are attributed to ν₂ and ν₄ bending modes confirming the reduction of the carbonate anion symmetry in the aurichalcite structure. This research proves that nickel containing aurichalcites can be synthesised in the laboratory thus mimicing the natural nickel containing aurichalcites.     

The application of polymer-bound carbonylcobalt(0) species in linker chemistry and catalysis

Carbonylcobalt(0) species have been used as linkers between alkynes and a polymer support for the first time. The alkynes may be loaded indirectly onto a phosphine functionalised polymer via their hexacarbonyldicobalt(0) complex, or directly onto a cobalt coated polymer. The alkynes have been released either as alkynes, thus providing a traceless method of immobilising alkynes, or by reaction with an alkene to generate a cyclopentenone via the Pauson-Khand reaction. The cobalt coated polymers produced during this study were shown to catalyse the Pauson-Khand reaction.     

The lateral stability of tractor and trailer combinations

A model has been developed to predict the lateral stability characteristics of tractor and unbalanced trailer combinations. For present combinations, stability deteriorates with speed culminating in instability at forward speeds in the region of 18 m/s. The effect of tractor and trailer size and other parameter variations on this speed dependent instability are examined.The effect of braking with and without axle locking are analysed. The stability of the combination is sensitive to the braking distribuion between the axles, which affect the hitch forces developed. Locking the tractor rear or trailer axle results in instabilities, commonly termed jack-knifing and trailer swing respectively. Jack-knifing is the more hazardous instability, whereas trailer swing although potentially dangerous has a divergence approximately an order of magnitude less.The potential of the model for predicting lateral dynamic behaviour of design concepts for future high speed farm transport which would operate at higher speeds than the current maximum of 9 m/s for tractor and trailer combinations is discussed. The scope for generalizing the model to examine other aspects of lateral behaviour, such as steering response is restricted by the limited amount of data available on the side force generated by tyres in agricultural conditions.     

Sphere Packing, III. Extremal Cases

This paper is the third in a series of six papers devoted to the proof of the Kepler conjecture, which asserts that no packing of congruent balls in three dimensions has density greater than the face-centered cubic packing. In the previous paper in this series, a continuous function f on a compact space was defined, certain points in the domain were conjectured to give the global maxima, and the relation between this conjecture and the Kepler conjecture was established. This paper shows that those points are indeed local maxima. Various approximations to f are developed, that will be used in subsequent papers to bound the value of the function f. The function f can be expressed as a sum of terms, indexed by regions on a unit sphere. Detailed estimates of the terms corresponding to triangular and quadrilateral regions are developed.     

The effect of temperature on the enthalpy of dilution of polyelectrolyte solutions

The integral enthalpies of dilution of sodium dextran sulphate and sodium alginate have been measured at 15, 25 and 40°. The results are compared with the predictions of the line charge theory. The experimental values show a much greater decrease with temperature than the calculated values and this difference is attributed to a contribution from solute/solvent interactions.     

Flaxseed Increases Animal Lifespan and Reduces Ovarian Cancer Severity by Toxically Augmenting One-Carbon Metabolism

We used an LC-MS/MS metabolomics approach to investigate one-carbon metabolism in the plasma of flaxseed-fed White Leghorn laying hens (aged 3.5 years). In our study, dietary flaxseed (via the activity of a vitamin B6 antagonist known as “1-amino d-proline”) induced at least 15-fold elevated plasma cystathionine. Surprisingly, plasma homocysteine (Hcy) was stable in flaxseed-fed hens despite such highly elevated cystathionine. To explain stable Hcy, our data suggest accelerated Hcy remethylation via BHMT and MS-B12. Also supporting accelerated Hcy remethylation, we observed elevated S-adenosylmethionine (SAM), an elevated SAM:SAH ratio, and elevated methylthioadenosine (MTA), in flaxseed-fed hens. These results suggest that flaxseed increases SAM biosynthesis and possibly increases polyamine biosynthesis. The following endpoint phenotypes were observed in hens consuming flaxseed: decreased physiological aging, increased empirical lifespan, 9–14% reduced body mass, and improved liver function. Overall, we suggest that flaxseed can protect women from ovarian tumor metastasis by decreasing omental adiposity. We also propose that flaxseed protects cancer patients from cancer-associated cachexia by enhancing liver function.