We compared the absorption of eicosapentaenoic (EPA, 20:5n-3), docosahexaenoic (DHA, 22:6n-3), and decanoic acids in mesenteric lymph duct-cannulated rats following intragastric administration of two oils with different intramolecular triacylglycerol structures. One oil had a specific triacylglycerol structure with EPA and DHA located in the sn-2 position and decanoic acid in the sn-1 and sn-3 positions (specific M-n3-M) whereas the other oil had a random fatty acid distribution (random M-n3-M). The mol% (mol/100 mol total fatty acids) of fatty acids in the two oils was similar, with approximately 66 mol% of decanoic acid and 22 mol% of EPA and DHA. The lymphatic transport (microgram/min) of EPA and DHA as well as the mol% in the total lymph lipids were significantly (both P < 0.01) increased following intragastric administration of specific M-n3-M compared with random M-n3-M. The mol% of decanoic acid in the total lymph lipids was significantly (P < 0.01) higher after random M-n3-M compared with specific M-n3-M but the transport (microgram/min) of decanoic acid was not significantly different. We conclude that under our experimental conditions specific M-n3-M with EPA and DHA predominantly in the sn-2 position of the triacylglycerols was a more readily absorbed source of EPA and DHA and in this context should be investigated further for the potential use in clinical nutrition.

Background: The Patient-Reported Outcomes version of the Common Terminology Criteria for Adverse Events is an item library designed for eliciting patient-reported adverse events in oncology. For each adverse event, up to three individual items are scored for frequency, severity, and interference with daily activities. To align the Patient-Reported Outcomes version of the Common Terminology Criteria for Adverse Events with other standardized tools for adverse event assessment including the Common Terminology Criteria for Adverse Events, an algorithm for mapping individual items for any given adverse event to a single composite numerical grade was developed and tested. Methods: A five-step process was used: (1) All 179 possible Patient-Reported Outcomes version of the Common Terminology Criteria for Adverse Events score combinations were presented to 20 clinical investigators to subjectively map combinations to single numerical grades ranging from 0 to 3. (2) Combinations with <75% agreement were presented to investigator committees at a National Clinical Trials Network cooperative group meeting to gain majority consensus via anonymous voting. (3) The resulting algorithm was refined via graphical and tabular approaches to assure directional consistency. (4) Validity, reliability, and sensitivity were assessed in a national study dataset. (5) Accuracy for delineating adverse events between study arms was measured in two Phase III clinical trials (NCT02066181 and NCT01522443). Results: In Step 1, 12/179 score combinations had <75% initial agreement. In Step 2, majority consensus was reached for all combinations. In Step 3, five grades were adjusted to assure directional consistency. In Steps 4 and 5, composite grades performed well and comparably to individual item scores on validity, reliability, sensitivity, and between-arm delineation. Conclusion: A composite grading algorithm has been developed and yields single numerical grades for adverse events assessed via the Patient-Reported Outcomes version of the Common Terminology Criteria for Adverse Events, and can be useful in analyses and reporting.

A method for the regiospecific analysis of triacylglyeerols (TAG), using the Grignard reagent allyl magnesium brm mide (AMB) to partially deacylate TAG, is described. 1,3-Distearoyl-2~leoyl~lycerol (SOS) and 1,3-dld~anoyl-2-pAlmitoyl-glycerol (CPC) were reacted with AMB. From the resulting mixture, the four different classes of partial acylglycerols and TAG were isolated, and the mole ratios between stearic acid and oleic acid, or decanoic acid and pslmitic acid, respectively, were determined in each fraction. Different approaches of calculating the composition of the fatty acids in positions sn-l(3) and sn-2 of the original TAG were compared. For the sn-2 position, the best estimate was the direct determination of the fatty acid composition of 2-monoacylglycerol (MAG). Mole percentages of stearic acid and decanoic acid in the sn-l(sn-3) positions of SOS and CPC, respectively, were most accurately estimated from the fatty acid compositions of TAG and 2-MAG according to the formula: 1.5 X TAG --0.5 X 2-MAG. Using AMB and the present method of calculation, the results obtained were more accurate and showed smaller standard deviations than those obtained using other common deacylating agents, such as ethyl magnesium bromide or pancreatic lipase.

Upon activation with (Et 3 O)PF 6 (2 equiv), the ruthenium(II) complex [RuCl 2 (PNNP)] (1; PNNP is (1S,2S)-N,N′-bis(o-(diphenylphosphino)benzylidene)cyclohexane-1,2-diamine) catalyzes the electrophilic fluorination of 1,3-dicarbonyl compounds by N-fluorobenzenesulfonimide (NFSI). Oxygen donors, in particular Et 2 O as cosolvent, increase the activity of the catalyst and, in some cases, the enantioselectivity. The absolute configuration of 2-tert-butoxycarbonyl-2-fluorocyclopentanone (5a), which is obtained with up to 93% ee in catalysis, was determined to be R by derivatization to (1S)-(-)-camphanic acid (1R,2R)-2-tert-butoxycarbonyl-2-fluoro-cyclopentyl ester (7) and X-ray analysis. A model for enantioselection is proposed on the basis of the known structures of the dicationic complex [Ru(4a)(PNNP)] 2+ (2a; 4a is 2-tert-butoxycarbonylcyclopentanone), which is formed under catalysis conditions, and of its monocationic enolato analogue (3a). The stoichiometric reactions of 2a and 3a with NFSI in pure CH 2 Cl 2 and in the presence of substrate, product, or Et 2 O show that proton-transfer processes promoted by oxygen donors are pivotal in catalysis. Scheme 1Scheme 2

Fluoride has recently found increasing application as coligand both in complexes of late transition metals and as a reagent in asymmetric catalysis. In recent papers, this topic was reviewed, with emphasis on the role played by so-called −push-pull interactions× between the fluoro ligand and a p acid in the stabilization of fluoro complexes with a d 6 or d 8 electron configuration. This picture has led to the concept that fluoride is the strongest p-donor in the halide series. Herein, the latter concept is discussed and criticized. In particular, the effect of the ionicity of the metal-fluoride bond is proposed as an alternative explanation to most of the observations that show a −reversed× halide order. The ionic character of the MÀF bond also accounts for its intrinsic reactivity and suggests some strategies for the stabilizatioin of fluoro complexes, including the use of coordinative unsaturation. The scope and limitations of the application of d 6 and d 8 fluoro complexes in catalysis are also discussed. The most promising application is the use of 16-electron fluoro complexes in the metal-promoted formation of the CÀF bond.