Optimized Quantitative Method for Determining Isoflavones and Equol in Bovine Digestive Fluids and Feces

Many studies have been conducted on the impact of animal feed on isoflavones and their metabolite concentrations in bovine milk, but few studies have focused on the development and validation of analytical protocols for quantifying these compounds in biological matrices other than milk and plants. The purpose of this study was to develop a method that would enable four isoflavones and equol in cows’ feces and digestive fluids to be quantified simultaneously. The method is based on aglycones released by methanolic ultrasound-assisted extraction, followed by enzymatic hydrolysis and high-performance liquid chromatography tandem–mass spectrometry analysis. The sample preparation was optimized using the Box–Behnken design. The selected extraction conditions were 80°C, 10?min, and 50% methanol for digestive fluids and 70°C, 35?min, and 60% methanol for feces. For hydrolysis, the selected conditions were 37°C, 1?h, and a pH of 6 for both matrices. The analytical method showed a good linear regression model ranging from 5 to 125?ng?mL^?1. Both inter- and intraday accuracy (≤8.5 and ≤12.3%) and precision (≤11.1 and ≤15.2%) were suitable. No matrix effects were found. There was good repeatability and extract stability for at least 4 days of storage at???20 and 6°C. All recoveries were in the acceptable range of 70–120% for both matrices, except for biochanin A in feces, where the value was approximately 43%. This sensitive and reliable method will be useful for monitoring the passage of isoflavones and equol in the digestive system of ruminants.     

CIDEP studies of the photolysis of the lignin model compound α-guaiacoxylacetoveratrone: the role of triplet reactions in aqueous and hydroxylic solvents

Free radical reactions induced by the photolysis of the lignin model compound α-guaiacoxylacetoveratrone have been studied by conventional and time-resolved ESR spectroscopy. In the presence of efficient hydrogen donors such as aqueous and hydroxylic solvents the primary reaction involves photoreduction of the triplet phenacyl ether to form the ketyl radical followed by rapid cleavage to the phenacyl radical and guaiacol. Subsequent formation of polarized guaiacoxyl radicals is due to secondary photo-oxidation. The cleavage of the ketyl radical is retarded in basic media and accelerated in acetic acid. Minor reaction pathways involving excited singlets cannot be ruled out by the current CIDEP observations.     

The Hopf conjecture for manifolds with low cohomogeneity or high symmetry rank

We prove that the Euler characteristic of an even-dimensional compact manifold with positive (nonnegative) sectional curvature is positive (nonnegative) provided that the manifold admits an isometric action of a compact Lie group with principal isotropy group and cohomogeneity such that . Moreover, we prove that the Euler characteristic of a compact Riemannian manifold or with positive sectional curvature is positive if admits an effective isometric action of a torus , i.e., if the symmetry rank of is .

     

Computer-aided design of chiral ligands. Part III. A novel ligand for asymmetric allylation designed using computational techniques

[reaction: see text] Computer-aided design protocols to identify new chiral ligands for reactions proceeding through well-defined transition states are outlined. Ligand families are discovered via computational screening of large structural databases such as the Cambridge Structural Database. Using this method, a novel cis-decalin ligand has been identified as a chiral auxiliary for the allylboration of aldehydes. Synthesis, resolution, and evaluation revealed that this new auxiliary provided the aldehyde facial approach upon which the design was predicated.     

A readily-accessible (+)-sparteine surrogate

A "(+)-sparteine-like" chiral diamine, readily synthesized in three steps from (-)-cytisine, has been evaluated in four different asymmetric transformations; in each case, selectivity in an enantiocomplementary fashion to (-)-sparteine was observed.     

Cosine modulated HSQC: a rapid determination of (3)J(HNHalpha) scalar couplings in (15)N-labeled proteins

A two-dimensional HSQC-based NMR method, (15)N-COSMO-HSQC, is presented for the rapid determination of homonuclear (3)J(HNHalpha) couplings in (15)N-labeled proteins in solution. Scalar couplings are extracted by comparing the intensity of two separate datasets recorded with and without decoupling of the (3)J(HNHalpha) during a preparation period. The scalar couplings are introduced through a cosine modulation of the peak intensities. The experiment relies on a BIRD sandwich to selectively invert all amide protons H(N) and is very simple to implement. (3)J(HNHalpha) couplings were determined using both the (15)N-COSMO-HSQC and quantitative-J on (15)N-labeled chemokine RANTES. The two experiments show well-correlated values.     

Maximal Convex Subgroups of the Automorphism Group of a Doubly Transitive Chain

We characterise all maximal convex l-subgroups of A(), the automorphismgroup of a doubly transitive chain of countable coterminality.We then determine, up to isomorphism, all doubly transitiveactions of the l-group A(). Finally, assuming the ContinuumHypothesis, we show that there exists an unbounded chain ofproper prime subgroups of A().     

Reversibly-formed ion pairs are not involved during the solvolysis of N,O-diacetyl-N-arylhydroxylamines

Appropriate oxygen-18 labeling experiments demonstrate that N,O-diarylhydroxylamines do not undergo solvolysis $\text{via}$ the reversible formation of ion pairs. This is in total conflict with the conclusions from previous indirect kinetic studies of these ultimate carcinogen models.