Actual ratios of triacylglycerol positional isomers and enantiomers comprising saturated fatty acids and highly unsaturated fatty acids in fishes and marine mammals.

It has been previously shown that the positional isomers of triacylglycerol (TAG) containing palmitic acid (P) and highly unsaturated fatty acids (HUFAs) such as DHA (D) and EPA (E) vary between fishes and marine mammals. However, it has not yet been understood why in marine mammals HUFAs are located only at the α position when two palmitic acid chains combine, and not in fishes. In order to gain further understanding of the biosynthetic pathways involved in the formation of these asymmetric TAGs, we investigated whether the HUFA in the TAG of marine mammals exists predominantly at the sn-1 or sn-3 position. We examined the TAG positional isomers and enantiomers in marine organisms in detail. As a result, while PDP and PEP were not detected, sn-PPD and sn-PPE were found in abundance in marine mammals. For fishes, on the other hand, PDP, PEP, sn-PPD, and sn-PPE were all identified. In the case of TAGs that contain two HUFAs and one palmitic acid, marine mammals were rich in DPD and EPE whereas fishes were rich in sn-PDD and sn-PEE.

Actual ratio of triacylglycerol positional isomers in milk and cheese.

Actual ratios of triacylglycerol (TAG) positional isomers in human, rat, and cow milk fat and cow, buffalo, goat, and sheep cheese fat were analyzed using HPLC-UV-atmospheric pressure chemical ionization-MS/MS system equipped with an octacosyl silylation column or polymeric ODS column. We substituted cheese fats for milk fats in parts of our study because milks from ruminants, with the exception of cows, are difficult to get in Japan. The actual ratio of ß-PPC (the TAG consisting of two palmitic acids (P) and one capric acid (C), with the palmitic acid located at the ß position) and ß-PCP in human milk was different from those in ruminants, with more than half of the medium-chain fatty acids located at the ß position even though other fats possessed it mainly at the α position. Palmitic acid was mainly located at the ß position for human milk and rat milk; however, the location in ruminant cheese fat was mainly at the α position. The location of fatty acids is thought to be very important for infant nutrition. Particularly, the location of palmitic acid in case of human milk and of medium-chain fatty acids in case of ruminant milk was very characteristic and is considered to be very important to the fatty acids in milk fat.

Rapid separation of triacylglycerol positional isomers binding two saturated Fatty acids using octacocyl silylation column.

The rapid separation of a triacylglycerol positional isomer (TAG-PI) pair was examined via high-performance liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry using an octacocyl silylation (C28) column. A TAG-PI pair binding two palmitic acids and one fatty acid that structurally differs from palmitic acid was separated at 10°C and 15°C using acetone as the mobile phase. However, the TAG-PI pair binding two unsaturated fatty acids and one saturated fatty acid was not separated by the C28 column. The results indicate that the structures of the two palmitic acids (saturated fatty acids) and the other fatty acid at the α or ß position in TAG play an important role in the separation of the TAG-PI pair, and that the structure of the fatty acid needs to be considerably different from that of the palmitic acid, specifically in terms of the chain length or the location of the double bond.

Enantiomeric separation of asymmetric triacylglycerol by recycle high-performance liquid chromatography with chiral column.

In our previous studies, we employed recycle HPLC for the separation of triacylglycerol (TAG)-positional isomers (PIs). In this study, a recycle HPLC system equipped with a polysaccharide-based chiral column was applied to the enantiomeric separation of some asymmetric TAGs having straight-chain C16-C18 acyl residues. As a result, 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (rac-PPO), 1,2-dioleoyl-3-palmitoyl-rac-glycerol (rac-OOP), and 1,2-dipalmitoyl-3-linoleoyl-rac-glycerol (rac-PPL) were resolved into their respective enantiomers. However, neither 1,2-dioleoyl-3-linoleoyl-rac-glycerol (rac-OOL), consisting of only unsaturated fatty acids, nor 1,2-dipalmitoyl-3-stearoyl-rac-glycerol (rac-PPS), consisting of only saturated fatty acids, was resolved. These results suggest that the asymmetric TAGs, used in this study, having both a palmitic acid moiety and an oleic acid (or a linoleic acid) moiety at the sn-1 or sn-3 positions are resolved by the chiral column. This new chiral separation method can be used in combination with atmospheric pressure chemical ionization mass spectrometry to determine the sn-OOP/sn-POO ratio in palm oil. This method is applicable for the chiral separation of asymmetric TAGs in palm oil.

Actual ratios of triacylglycerol positional isomers consisting of saturated and highly unsaturated fatty acids in fishes and marine mammals.

The distribution of fatty acid species at the (sn-1, 3) position or the (sn-2) position of triacylglycerol (TAG) in natural fats and oils has already been analysed by many researchers and several interesting results have been reported. However, most of these reports only focused on the distribution of fatty acids at the or positions in TAG, and did not take account of the combination of fatty acids in the TAG, i.e., the TAG positional isomers. In this study, the actual ratios of TAG positional isomer pairs, consisting of palmitic acid and highly unsaturated fatty acid (HUFA) such as DHA or EPA, in fish and marine mammals were investigated using a high-performance liquid chromatography/atmospheric pressure chemical ionisation-mass spectrometry (HPLC/APCI-MS) system equipped with tandem jointed non-endcapped polymeric ODS columns. The results show that for combinations of DHA or EPA with two palmitic acids in the TAG of marine mammals, binding was almost all at the α position. In contrast, binding of DHA or EPA was mainly at the ß position in fish. The preferred DHA and EPA positions in TAG were the same in the same marine mammal or fish. The binding position tendency of HUFA in TAG positional isomers consisting of two HUFAs and one palmitic acid was the same as that for combinations of one HUFA and two palmitic acids. These results were interpreted as showing that the preferred fatty acid species of sn-glycerol-3-phosphate acyltransferase and 1-acyl-sn-glycerol-3-phosphate acyltransferase in marine mammals are different to those in fish and other animals, or that diacylglycerol acyltransferase in marine mammals favours 1,2-dipalmitoyl-sn-glycerol formed from 1,2-dipalmitoyl-sn-glycerol-3-phosphatidate if HUFA is the reaction substrate.

Characterization of non-endcapped polymeric ODS column for the separation of triacylglycerol positional isomers.

The characteristics of a non-endcapped polymeric ODS column for the resolution of triacylglycerol positional isomers (TAG-PI) were examined using a recycle HPLC-atmospheric pressure chemical ionization/mass spectrometry system. A pair of TAG-PI containing saturated fatty acids at least 12 carbons was separated. Except for TAG-PI containing elaidic acid, pairs of TAG-PI containing three unsaturated fatty acids were not separated, even by recycle runs. These results indicate that the resolution of TAG-PI on a non-endcapped polymeric ODS stationary phase is realized by the recognition of the linear structure of the fatty acid and the binding position of the saturated fatty acid in TAG-PI. Chain length was also an important factor for resolution. This method may be a useful and simple for measuring the abundance ratio of TAG-PI containing saturated fatty acids in natural oils.

Variance analysis of a clinical pathway of video-assisted single lobectomy for lung cancer.

PURPOSE: Clinical pathways have contributed to standardized postoperative management, but analyzing variance is also important to maintain quality control. To evaluate the validity of our own clinical pathway for managing video-assisted lobectomy for lung cancer, we analyzed the variances influencing postoperative recovery. METHODS: Between April 2003 and April 2004, 62 consecutive patients with lung cancer underwent video-assisted single anatomic lobectomy with lymph node dissection. We evaluated 61 of these patients after the exclusion of one, who deviated from the clinical pathway management immediately as a result of serious complications. RESULTS: There were 29 men and 32 women, with an average age of 65.7 years. Complications developed in 29 patients, but there was no operative mortality. The occurrence of variance ranged from 1.6% to 34.4% for each activity and included prolonged supplemental oxygen therapy, out-of routine examination, prolonged epidural anesthesia, and delayed bathing frequently. Complications and an abnormal body mass index were significant and independent clinical factors affecting the increase in variance. CONCLUSIONS: Our original clinical pathway management was tolerable for lung cancer patients undergoing a video-assisted lobectomy. Complications and an abnormal body mass index were significant predictive factors for an increase in variance of our clinical pathway.

Successful recovery from a massive pulmonary artery tumor embolism occurring during surgery for renal cell carcinoma.

We report herein on a case of renal cell carcinoma with retrohepatic inferior vena cava tumor thrombus in which intraoperative cardiac arrest from a massive pulmonary embolism was managed successfully with emergency sternotomy and cardiopulmonary bypass, followed by the removal of the primary site and pulmonary artery embolus.