Benzoxazinoids in Prostate Cancer Patients after a Rye-Intensive Diet: Methods and Initial Results.

Rye bread contains high amounts of benzoxazinoids, and in vitro studies have shown suppressive effects of selected benzoxazinoids on prostate cancer cells. Thus, research into benzoxazinoids as possible suppressors of prostate cancer is demanded. A pilot study was performed in which ten prostate cancer patients received a rye-enriched diet 1 week prior to prostatectomy. Plasma and urine samples were collected pre- and postintervention. Ten prostate biopsies were obtained from each patient and histologically evaluated. The biopsies exhibited concentrations above the detection limit of seven benzoxazinoids ranging from 0.15 to 10.59 ng/g tissue. An OPLS-DA analysis on histological and plasma concentrations of benzoxazinoids classified the subjects into two clusters. A tendency of higher benzoxazinoid concentrations toward the benign group encourages further investigations. Benzoxazinoids were quantified by an optimized LC-MS/MS method, and matrix effects were evaluated. At low concentrations in biopsy and plasma matrices the matrix effect was concentration-dependent and nonlinear. For the urine samples the general matrix effects were small but patient-dependent.

Cinnamoylphenethylamine 1H-NMR chemical shifts: a concise reference for ubiquitous compounds.

1H-NMR data of 25 cinnamoylphenethylamine derivates were recorded and compared in order to assign signals unequivocally without additional spectroscopic data. The spectra provide a key for the rapid identification of these ubiquitous natural products. The compounds isomerize rapidly in UV light, producing a characteristic upfield shift of the olefinic protons consistent with distorted planarity of the cis cinnamate, and this requires special attention during preparative work.

Synthesis and quantitation of six phenolic amides in Amaranthus spp.

Cinnamoylphenethylamines are phenolic amides in which cinnamic acid provides the acid moiety and phenethylamine the amine moiety. Single ion monitoring (SIM) in LC-MS was performed on amaranth leaf extracts. Masses corresponding to sets of regioisomers, including previously reported compounds, were examined. Six peaks were detected and their corresponding standards synthesized for a quantitative LC-MS/MS investigation of cinnamoylphenethylamines in amaranth. Four cinnamoylphenethylamines (caffeoyltyramine, feruloyldopamine, sinapoyltyramine, and p-coumaroyltyramine) are reported in the Amaranthaceae for the first time; also, one rare compound, feruloyl-4-O-methyldopamine, appeared to be quite common in the genus Amaranthus. Feruloyldopamine showed moderate antifungal activity toward an isolate of Fusarium culmorum. Our LC-MS approach, in conjunction with the straightforward synthesis, provides a simple, reliable way of quantitatively investigating cinnamoylphenethylamines in plants. Concentrations of cinnamoylphenethylamines vary widely: feruloyltyramine was present in quantities of 5.26 to 114.31 microg/g and feruloyldopamine in quantities of 0.16 to 10.27 microg/g, depending on the plant sample.