Paramagnetic 1H-NMR relaxation probes of stereoselectivity in metalloporphyrin catalyzed olefin epoxidation

Enantioselective catalytic epoxidation of olefins is an important problem from both practical and mechanistic points of view. The origins of chiral induction by asymmetric porphyrin and salen complexes were investigated by FT-NMR T1 relaxation techniques. A new chiral vaulted porphyrin (1) that carries (S)-binaphthyl-L-alanine straps across both faces of the porphyrin macrocycle was synthesized and characterized. (R)-styrene oxide was obtained in > 90% ee in the initial stages of styrene epoxidation with F5PhIO catalyzed by 1-Fe(III)Cl. The transition state for olefin epoxidation with high-valent metal-oxo species was modeled by coordinating epoxides to paramagnetic copper complexes of the corresponding ligands. The epoxide enantiomer that better fit the chiral cavity of the catalyst, as revealed by T1 relaxation measurements, was also the major product of catalytic olefin epoxidation. These results are consistent with the "lock-and-key" mechanism of asymmetric catalysis by metalloporphyrins. The copper complex of a chiral salen ligand showed no differentiation in terms of T1 relaxation rates between the enantiomers of cis-beta-methylstyrene oxide in contrast to the high enantioselectivity observed for catalytic epoxidation.     

Lipid peroxidation in patients with ischemic heart disease, hyperlipidemia and/or hypertension while polyunsaturated omega-3 fatty acids of plant and animal origin were in their diet

Missing anterior teeth are being replaced by implant-supported restorations quite frequently in modern dentistry. Providing the patient with a temporary prosthesis prior to or following implant fixture placement must satisfy established esthetic and functional criteria. When orthodontic treatment is included as part of the overall treatment effort, additional considerations include the retention and stabilization of newly established tooth positions. This article describes the fabrication, use and advantages of a provisional anterior prosthesis that replaces missing teeth prior to or following implant placement.     

Yoga breathing through a particular nostril increases spatial memory scores without lateralized effects

Uninostril breathing facilitates the performance on spatial and verbal cognitive tasks, said to be right and left brain functions, respectively. Since hemispheric memory functions are also known to be lateralized, the present study assessed the effects of uninostril breathing on the performance in verbal and spatial memory tests. School children (N = 108 whose ages ranged from 10 to 17 years) were randomly assigned to four groups. Each group practiced a specific yoga breathing technique: (i) right nostril breathing, (ii) left nostril breathing, (iii) alternate nostril breathing, or (iv) breath awareness without manipulation of nostrils. These techniques were practiced for 10 days. Verbal and spatial memory was assessed initially and after 10 days. An age-matched control group of 27 were similarly assessed. All 4 trained groups showed a significant increase in spatial test scores at retest, but the control group showed no change. Average increase in spatial memory scores for the trained groups was 84%. It appears yoga breathing increases spatial rather than verbal scores, without a lateralized effect.     

Porphyrobacter tepidarius sp. nov., a moderately thermophilic aerobic photosynthetic bacterium isolated from a hot spring

BACKGROUND: The epidemic of Human Immunodeficiency Virus (HIV) infection led blood banks to initiate donation deferral criteria based on self-reported risk factors. However little information is available on the differences in reporting risk factors before and after HIV status is known. METHODS: Between April and July 1994, blood donors in a provincial hospital in northern. Thailand were interviewed at the time of donation, about their demographic characteristics and risk factors. All donors had agreed to learn their test results and were called back for post-test counselling and reinterview. RESULTS: HIV-positive blood donors were more likely to change from 'denying' to 'acknowledging' risk factors while HIV-negatives were more likely to change from 'acknowledging' to 'denying'. The differences between risk factors obtained before and after test results were known resulted in stronger, weaker or even opposite risk measures. CONCLUSION: The study results raise questions about the impact of the differences in reporting HIV-related risk factors by the donors on how effective donation deferral criteria can be developed.     

Paradoxical cerebral emboli after transjugular intrahepatic portosystemic shunt and coil embolization for treatment of duodenal varices

The use of the transjugular intrahepatic portosystemic shunt to treat portal hypertension has resulted in increased recognition of its associated complications. We report a patient with refractory duodenal variceal bleeding treated with transjugular intrahepatic portosystemic shunt, as well as coil embolization, who subsequently developed bilateral cerebral and cerebellar infarcts consistent with arterial emboli. This complication has not been previously described. The patient was found to have a patent foramen ovale and a right to left intracardiac shunt leading to paradoxical embolization of clots traveling from portal to systemic venous circulation, then to the left atrium. With the relative frequency of patent foramen ovale in the population, our observation has potential importance for patients with right to left cardiac shunts who are being considered for portosystemic shunt procedures, or who are undergoing embolization of bleeding varices.     

Evaluation of 7,000+ patients with two different routes of cardioplegia

BACKGROUND: This study examined the efficacy and safety of retrograde cardioplegia in comparison with an antegrade/retrograde approach. METHODS: Between January 1, 1991, and December 31, 1995, 7,032 coronary artery bypass procedures, alone or in combination with valve replacement/repair, were performed using either retrograde cardioplegia (R) or an antegrade/retrograde (AR) approach. There were 4,224 patients in the R group and 2,808 in the AR group. These included elective, urgent, emergent/salvage, first operative, and redo cases. RESULTS: All preoperative, intraoperative, and postoperative variables listed in The Society of Thoracic Surgeons National Cardiac Surgery Database were used to compare the two groups using univariate analysis. The pump time was longer in the AR group, with fewer grafts per patient. The R group had higher predicted risk (3.2% versus 3.0%; p = 0.04), more postoperative atrial fibrillation (34% versus 31%; p = 0.006), and longer postoperative length of stay (8.8 versus 8.0 days; p < 0.001). Using The Society of Thoracic Surgeons National Cardiac Surgery Database predicted risk group model, a subgroup of 221 coronary artery bypass grafting patients in the retrograde (s-R) and 132 coronary artery bypass grafting patients in the antegrade/retrograde (s-AR) group fell into a greater incidence of predicted mortality group (> or = 10%). The s-R subgroup had more patients in New York Heart Association functional class IV. Univariate analysis revealed higher postoperative atrial fibrillation (51% versus 41%; p = 0.05) and longer postoperative length of stay (12.8 versus 10.8 days; p = 0.03) in the s-R subgroup versus the s-AR subgroup. CONCLUSIONS: The results appear to favor neither approach. Preoperatively, both retrograde groups (R and s-R) had higher preoperative predicted risk, but operative mortality or complications were not significantly increased when compared with the AR and s-AR groups. Retrograde cardioplegia alone was shown to be effective in the R and s-R groups, but atrial fibrillation developed in more patients, which could have contributed to longer length of stay in these groups. Antegrade/retrograde cardioplegia offers good immediate outcome but the delivery method can be cumbersome and confusing during the adjustments of flow clamps for antegrade/retrograde delivery and may contribute to prolonged pump times. From this retrospective, nonrandomized review, it appears that retrograde cardioplegia alone provides as good myocardial protection and safety as an antegrade/retrograde approach in either the low-risk or high-risk patient.     

Antigen therapy eliminates T cell inflammation by apoptosis: effective treatment of experimental autoimmune neuritis with recombinant myelin protein P2

Exposure of T cells to their specific antigen normally results in proliferation, but in the presence of high and repeatedly administered doses of antigen, T cells may undergo apoptosis. Here we demonstrate that i.v. administration of as little as 100 microg of recombinant P2 protein twice daily completely prevents experimental autoimmune neuritis induced by adoptive transfer of neuritogenic P2-specific T cells or by immunization with the neuritogenic P2-peptide-spanning amino acids 53-78. Antigen treatment started after disease onset markedly ameliorated experimental autoimmune neuritis. The mechanism of action may be through programmed T cell death; a profound increase of the rate of apoptosis was seen in inflammatory foci of peripheral nerves and in the spleen. There was no cytokine switch by our Th1 cells after exposure to their specific antigen, but increased secretion of interferon gamma and tumor necrosis factor alpha was demonstrated. High antigen dose therapy using recombinant, pathogen-free protein may prove useful for the treatment of autoimmune inflammatory disorders of the nervous system.     

Design of constructions for the expression of proteolytic antibody light chain

A new system for the expression of a catalytic light chain antibody to the vasoactive intestinal peptide is described. The system made possible the isolation the large amounts of a homogeneous protein without any additional peptide domains. The preparation obtained can be used in further experiments on light chain crystallization and in X-ray-structural analysis of its catalytic center.