Asymmetric diosmium sawhorse complexes.

Three asymmetric diosmium(I) carbonyl sawhorse complexes have been prepared by microwave heating. One of these complexes is of the type Os2(µ-O2CR)(µ-O2CR')(CO)4L2, with two different bridging carboxylate ligands, while the other two complexes are of the type Os2(µ-O2CR)2(CO)5L, with one axial CO ligand and one axial phosphane ligand. The mixed carboxylate complex Os2(µ-acetate)(µ-propionate)(CO)4[P(p-tolyl)3]2, (1), was prepared by heating Os3(CO)12 with a mixture of acetic and propionic acids, isolating Os2(µ-acetate)(µ-propionate)(CO)6, and then replacing two CO ligands with two phosphane ligands. This is the first example of an Os2 sawhorse complex with two different carboxylate bridges. The syntheses of Os2(µ-acetate)2(CO)5[P(p-tolyl)3], (3), and Os2(µ-propionate)2(CO)5[P(p-tolyl)3], (6), involved the reaction of Os3(CO)12 with the appropriate carboxylic acid to initially produce Os2(µ-carboxylate)2(CO)6, followed by treatment with refluxing tetrahydrofuran (THF) to form Os2(µ-carboxylate)2(CO)5(THF), and finally addition of tri-p-tolylphosphane to replace the THF ligand with the P(p-tolyl)3 ligand. Neutral complexes of the type Os2(µ-O2CR)2(CO)5L had not previously been subjected to X-ray crystallographic analysis. The more symmetrical disubstituted complexes, i.e. Os2(µ-formate)2(CO)4[P(p-tolyl)3]2, (8), Os2(µ-acetate)2(CO)4[P(p-tolyl)3]2, (4), and Os2(µ-propionate)2(CO)4[P(p-tolyl)3]2, (7), as well as the previously reported symmetrical unsubstituted complexes Os2(µ-acetate)2(CO)6, (2), and Os2(µ-propionate)2(CO)6, (5), were also prepared in order to examine the influence of axial ligand substitution on the Os-Os bond distance in these sawhorse molecules. Eight crystal structures have been determined and studied, namely µ-acetato-1κO:2κO'-µ-propanoato-1κO:2κO'-bis[tris(4-methylphenyl)phosphane]-1κP,2κP'-bis(dicarbonylosmium)(Os-Os) dichloromethane monosolvate, [Os2(C2H3O2)(C3H5O2)(C21H21P)2(CO)4]·CH2Cl2, (1), bis(µ-acetato-1κO:2κO')bis(tricarbonylosmium)(Os-Os), [Os2(C2H3O2)2(CO)6], (2) (redetermined structure), bis(µ-acetato-1κO:2κO')pentacarbonyl-1κ2C,2κ3C-[tris(4-methylphenyl)phosphane-1κP]diosmium(Os-Os), [Os2(C2H3O2)2(C21H21P)(CO)5], (3), bis(µ-acetato-1κO:2κO')bis[tris(4-methylphenyl)phosphane]-1κP,2κP-bis(dicarbonylosmium)(Os-Os) p-xylene sesquisolvate, [Os2(C2H3O2)2(C21H21P)2(CO)4]·1.5C8H10, (4), bis(µ-propanoato-1κO:2κO')bis(tricarbonylosmium)(Os-Os), [Os2(C3H5O2)2(CO)6], (5), pentacarbonyl-1κ2C,2κ3C-bis(µ-propanoato-1κO:2κO')[tris(4-methylphenyl)phosphane-1κP]diosmium(Os-Os), [Os2(C3H5O2)2(C21H21P)(CO)5], (6), bis(µ-propanoato-1κO:2κO')bis[tris(4-methylphenyl)phosphane]-1κP,2κP-bis(dicarbonylosmium)(Os-Os) dichloromethane monosolvate, [Os2(C3H5O2)2(C21H21P)2(CO)4]·CH2Cl2, (7), and bis(µ-formato-1κO:2κO')bis[tris(4-methylphenyl)phosphane]-1κP,2κP-bis(dicarbonylosmium)(Os-Os), [Os2(CHO2)2(C21H21P)2(CO)4], (8).

In vitro studies regarding the feasibility of bovine erythrocyte xenotransfusion.

Pigs are considered the most likely source of organs and tissues should the barriers to xenotransplantation be overcome. The use of animal blood for transfusion, xenotransfusion, would have advantages over blood from random human donors with respect to supply and infection control. Large animals such as cows would be more suitable than pigs for blood donation because of easier venous access and large volume phlebotomy. Blood from 12 Holstein cows was typed and then tested for hemagglutination assay (HA), complement mediated lysis (CML), human IgM and IgG antibody binding, anti-human globulin augmented clinical cross-match and osmotic fragility with normal human serum. Results were compared with porcine erythrocytes (pRBC) and with human type O controls (hRBC). The frequency of ultra-low xenoantigen expressors was tested in a larger herd of various breeds using HA and CML. Median HA and CML titers were one of six (no HA-one of 64) and one of 26 (no CML-one of 64), respectively for bovine erythrocytes (bRBC). Hemagglutination titer was significantly higher for pRBC at one of 170 (one of four-one of 1024). HA and CML were lowest with bovine blood group J. Repeated HA and CML were negative with bRBC from one cow that also tested negative by anti-human globulin augmented cross-match with seven of nine random human sera representing the different blood groups. However, flow cytometry showed that bRBC from all cows bound human IgM and IgG. IgM mean channel fluorescence (MCF) was positively correlated with HA titer. The mean corpuscular fragility of pRBC, bRBC, and hRBC was 0.56, 0.48 and 0.41%, respectively. The frequency of HA-negative and CML-negative cows were 20 and 35%, respectively in herds of 49 animals. Bovine RBC elicit variable in vitro responses from human serum but these are uniformly much less than those seen with pRBC. Bovine RBC is more robust than pRBC. These characteristics including the potential ease and volume of blood collection make the cow a more suitable blood donor than the pig.

Evaluating porcine RBC and platelet alpha-galactosyl expression.

BACKGROUND: Naturally occurring human xenoreactive antibodies bind and agglutinate porcine RBCs. STUDY DESIGN AND METHODS: To determine if xenoantigen expression on RBCs of individual pigs of different breeds and blood groups is variable, and if it correlates with platelet (PLT) expression, we measured adsorption of affinity-purified antibodies to alpha-galactosyl (alphaGal) by RBCs or PLTs from 22 pigs representing four breeds. Hemagglutination of RBCs from these pigs was also performed with pools of human group OAB, A, B, and AB sera, as well as with anti-alphaGal-depleted pooled OAB human serum. RESULTS: There was significant variation in alphaGal expression on RBCs and PLTs among pigs. PLT alphaGal expression did not correlate with RBC alphaGal. RBCs from all pigs were agglutinated by pooled group O, AB, A, or B sera, whereas titers were reduced by 87 percent with anti-alphaGal-depleted serum and by 82 percent with AB sera from two volunteers. Agglutination titers were higher against RBCs from the five highest RBC alphaGal expressers compared with those from the five lowest RBC alphaGal expressers (92 +/- 12 vs. >160, p < 0.05, where 160 was the maximum dilution tested). CONCLUSION: Hemagglutination is a feasible alternative for rapid identification of pigs with RBCs carrying less alphaGal.