A Proposed Stereochemical Mechanism for the Improved Preparation of Maleic Anhydride Cycloadduct of CLA

The fatty acid derivatives, prepared from renewable natural oils, can be used as highly promising and potential substitutes for petrochemicals. The study of process improvement and stereochemical mechanism for preparing these derivatives would be beneficial for their industrial production. Conjugated linoleic acid (CLA) containing 9cis-11trans (9c, 11t) and 10trans-12cis (10t, 12c) isomers was prepared from Salicornia herbacea seed oil. Maleic anhydride cycloadduct of CLA (MAC) was prepared by an improved process, and it was characterized by FTIR, 1H and 13C NMR, etc. A new method to calculate conformers-ratio of CLA or MAC was also developed. Furthermore, the stereochemical mechanism for the improved preparation of MAC was proposed primarily by the calculation method above. The following observations were made: 1) The yield of MAC could reach as high as 96.7% under mild reaction conditions and with an easy and efficient product separation;2) The trans-trans CLA in the s-cis conformation acted as a predominant reactant to Diels-Alder [4 + 2] cycloaddition of maleic anhydride, which was the main reaction occurred simultaneously with catalytic configurational isomerizations of CLA in one step;3) From all studied CLA conformers, the most stable conformation was the s-trans conformation of trans-trans CLA, while the s-cis conformation of trans-trans CLA had the most favorable structural parameters for cyclohexenyl ring formation;4) Four MAC conformers derived from 9c, 11t- and 10t, 12c-CLA, were obtained as final main products that were determined to be cis-cycloadducts;5) The endo/exo ratios of the cis- cycloadducts derived from 9c, 11t- and 10t, 12c-CLA, were 2.14:1 and 1.99:1, respectively;and 6) The results obtained from the calculation method above were in excellent accordance with those from our experiments.

Colometer:A real-time quality feedback system for screening colonoscopy

AIM:To investigate the performance of a new software-based colonoscopy quality assessment system.METHODS:The software-based system employs a novel image processing algorithm which detects the levels of image clarity,withdrawal velocity,and level of the bowel preparation in a real-time fashion from live video signal.Threshold levels of image blurriness and the withdrawal velocity below which the visualization could be considered adequate have initially been determined arbitrarily by review of sample colonoscopy videos by two experienced endoscopists.Subsequently,an overall colonoscopy quality rating was computed based on the percentage of the withdrawal time with adequate visualization(scored 1-5;1,when the percentage was 1%-20%;2,when the percentage was 21%-40%,etc.).In order to test the proposed velocity and blurriness thresholds,screening colonoscopy withdrawal videos from a specialized ambulatory colon cancer screening center were collected,automatically processed and rated.Quality ratings on the withdrawal were compared to the insertion in the same patients.Then,3 experienced endoscopists reviewed the collected videos in a blinded fashion and rated the overall quality of each withdrawal(scored 1-5;1,poor;3,average;5,excellent) based on 3 major aspects:image quality,colon preparation,and withdrawal velocity.The automated quality ratings were compared to the averaged endoscopist quality ratings using Spearman correlation coefficient.RESULTS:Fourteen screening colonoscopies were assessed.Adenomatous polyps were detected in 4/14(29%) of the collected colonoscopy video samples.As a proof of concept,the Colometer software rated colonoscope withdrawal as having better visualization than the insertion in the 10 videos which did not have any polyps(average percent time with adequate visualization:79% ± 5% for withdrawal and 50% ± 14% for insertion,P < 0.01).Withdrawal times during which no polyps were removed ranged from 4-12 min.The median quality rating from the automated system and the reviewers was 3.45 [interquartile range(IQR),3.1-3.68] and 3.00(IQR,2.33-3.67) respectively for all colonoscopy video samples.The automated rating revealed a strong correlation with the reviewer's rating(ρ coefficient= 0.65,P = 0.01).There was good correlation of the automated overall quality rating and the mean endoscopist withdrawal speed rating(Spearman r coefficient= 0.59,P = 0.03).There was no correlation of automated overall quality rating with mean endoscopists image quality rating(Spearman r coefficient= 0.41,P = 0.15).CONCLUSION:The results from a novel automated real-time colonoscopy quality feedback system strongly agreed with the endoscopists' quality assessments.Further study is required to validate this approach.

AN IMPROVED METHOD FOR PREPARING 2—ALKOXY—5—FLUORO—3H—4—PYRIMIDONE~△

In this paper, we report an improved method for preparing 2--alkoxy 5 fluoro--3H --4--pyrimidone from 2--chloro--5--fluoro--3H--4--pyrimidone and sodium alkoxide under normal pressure at reflux temperature. Some new compounds were synthesized in higher yield by this method.