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This study is a first step approach towards the prediction of the proportion of grassland-based feeds (%GB) in dairy cow diets with the aid of three different groups of milk biomarkers. We aimed to evaluate and quantify the associations between biomarkers commonly suggested in the literature and %GB in individual cows as a hypothesis-generating stage for the prospective establishment of accurate %GB prediction models. Consumers and governments financially encourage sustainable, local milk production making grass-based feeding, in grassland-dominated regions, of major interest. Milk from grassland-fed cows differs from that of other feeding systems by inferential fatty acids (FA), β-carotene content and yellow color; however, these biomarkers have not been evaluated together for their association with %GB. Using approved methods of parametric regression analysis, gas chromatography (GC), mid-infrared spectra (MIR) and color spectroscopy, we aimed to develop a first step towards an easy-to-implement, cost-effective milk-based control to estimate %GB in dairy cow diets. The underlying database was generated with 24 cows each fed one of 24 different diets gradually increasing in grass silage and decreasing in corn silage. Our results indicate that GC-measured α-linolenic acid, total n-3 FA and the n-6:n-3 ratio, MIR-estimated PUFA and milk red-green color index a* are robust milk biomarkers for constructing accurate prediction models to determine %GB. Based on simplified regression analysis, diets containing 75% GB should contain ≥ 0.669 and 0.852 g α-linolenic acid and total n-3 FA per 100 g total FA, respectively, and an n-6:n-3 FA ratio of < 2.02 measured with GC; estimated with MIR, polyunsaturated FA should be ≥ 3.13 g/100 g total FA. β-carotene was not a good predictor for estimating %GB. Unexpectedly, the milk became greener with increasing %GB (negative a* values, ‒6.416 for 75% GB), suggesting the red-green color index, not yellow-blue, as a suitable biomarker.

A C₂-symmetric enantiopure 4,5-bis(pinene)-2,2′-bipyridine ligand (–)-L was used to investigate the diastereoselectivity in the formation of [ML₃]²⁺ coordination species (M = Fe(II), Ru(II), Os(II), Zn(II), Cd(II), Cu(II), Ni(II)), and [ML₂Cl₂] (M = Ru(II), Os(II)). The X-ray structures of the [ML₃]²⁺ complexes were determined for Δ-[FeL₃](PF₆)₂, Δ-[RuL₃](PF₆)₂, Λ-[RuL₃](PF₆)₂, Δ-[OsL₃](PF₆)₂, and Λ-[OsL₃](TfO)₂. All of these compounds were also characterized by NMR, CD and UV/VIS absorption spectroscopy. The [FeL₃]²⁺ diastereoisomers were studied in equilibrated solutions at various temperatures and in several solvents. The [RuL₃]²⁺ complexes, which are thermally stable up to 200 °C, were photochemically equilibrated.