The terminal carbohydrate chain of blood group substances of the ABO system represent the determinant structure of the antigen responsible for the high immunological specificity of these glycoproteins[ 'I. After having developed a new stereoselective method for the preparation of a-glycosidically linked 2-amin0-2-deoxy-D-galactose[~~, we have now succeeded in synthesizing the terminal carbohydrate chains of the blood group substances A, B, and H.As starting substance we used the readily accessible disaccharide benzyl-2-acetamido-3-0-(2,3,4,6-tetra-0-acetyl-~-~-galactopyranosyl)-4,6-0-benzyl~dene-2-deoxy-a-~-glucopyranosideC3], which after selective cleavage of the 0-acetyl groups and subsequent reaction with benzaldehyde affords the bis-(benzylidene) compound (1 ).(1 ) can be selectively benzoylated at the OH group on C-3 to give (2,P4]. The fucose residue can then be linked to the remaining 2'-OH group of (2) by reaction with the bromide (3) to give (6) in 82 % yield. On halide ion catalysis this reaction affords only the a-LThe 3'-OH group can be released again by selective alkaline hydrolysis with formation of (7). Complete deblocking by hydrogenation affords the chain (10) of the H substance (Type 1)[51 ([a];'= -15.4") in 74% yield based on (7). The trisaccharide (7) can react directly with the a-bromide (8), and, in the presence of Hg(CN)z/HgBrz, yields the a -~-linked tetrasaccharide ( 4 ) in 63 % yield. The inversion technique generally used by us[2,61 [conversion of (8) into the P-chloride and subsequent transformation into the a-glycoside] is unnecessary in this reaction. The tetrasaccharide chain (5) of the blood group substance A (Type 1) ([a];" = 53.8") can be obtained i n 77% yield (based on ( 4 ) ) from ( 4 ) by deblocking with sodium methoxide and hydrogenolytic cleavage.The blood group substance B can be obtained in the same way from the trisaccharide (7). The galactosyl bromide ( 9 ) reacts with (7) in the presence of Hg(CN)2'71 also to give the a-D-linked tetrasaccharide (1 1) (in 73 % yield). The tetrasaccharide chain (12) of the blood group substance B (type 1) ([a];'=33.3") is obtainable from (11) in a deblocking step by hydrogenolytic cleavage with Pd/C in glacial acetic acid (yield 82% based on (11)).
Summary The blood of a Puerto Rican, of a West Indian Negress and of several members of a Baltimore Negro family is described. The red cells of these people are apparently of the phenotype i and their serum contains anti‐I. The samples differ somewhat from that of the English i donor of Jenkins et al. (1960): their red cells are not quite so weak in I antigen and the anti‐I in their serum is more restricted in range. The anti‐I in the serum of the Puerto Rican is outstanding because it contains what may be called a pseudo anti‐A1. None of the five anti‐I sera described in this paper agglutinates cord cells. I seems to be a graded character, in this respect somewhat like H; its possible relationship to other systems is discussed. The Baltimore family provides the first evidence that the I antigen is under genetic control. Résumé Les auteurs décrivent les sangs d'un portoricain, d'une femme de race noire de l'Inde occidentale et de plusieurs membres d'une famille de race noire de Baltimore. Les érythrocytes de ces personnes sont vraisemblablement du phénotype i et leur sérum contient de l'anti‐I. Ces sangs diffèrent quelque peu de celui du donneur anglais de phénotype i décrit par Jenkins et al. (1960): la contenance en anti‐gène I e leurs érythrocytes n'est pas aussi faible et l'anti‐I présent dans leur sérum se révèle avoir un champ d'activité de moindre importance. En outre, l'anti‐I du sérum du sujet portoricain présente la particularité de contenir ce que Yon peut appeler un pseudo anti‐A1. Aucun des cinq anti‐I décrits clans ce travail n'agglutine les érythrocytes provenant du sang du cordon. L'antigène I semble être un caractere se manifestant à des degrés de force diverse, comme l'antigène H; les auteurs discutent des rapports possibles de cet antigène avec les antigènes d'autres systèmes. La famille de Baltimore apporte pour la première fois la preuve que l'antigène I est conditionné selon les lois de la génétique. Zusammenfassung Die Blutproben eines Spenders aus Puerto Rico, einer westindischen Negerin und diejenigen einer Negerfamilie aus Baltimore werden beschrieben. Die Erythrozyten dieser Individuen weisen offensichtlich den Phänotypus i auf; ihr Serum enthält Anti‐I‐Antikörper. Die Blutproben zeigen gegenüber derjenigen des englischen von Jenkins et al. (1960) beschriebenen Spenders gewisse Unterschiede. Der Gehalt an I‐Antigen dieser Zellen war nicht ganz so gering wie beim erwähnten englischen Spender. Auch war der Wirkungsbereich ihrer Anti‐I‐Seren geringer als beim englischen Spender Als Besonderheit enthielt das Anti‐I‐Serum des Spenders aus Puerto Rico eine Antikörperfraktion, welche als Pseudo‐Anti‐A1 zu bezeichnen ist Keines der 5 in dieser Arbeit erwähnten Seren vermochte Nabel‐schnurerythrozyten zu agglutinieren Beim I‐Antigen handelt es sich ähnlich wie beim H‐Antigen um eine Blutgruppeneigenschaft, die in den Erythrozyten in wechselnder Stärke enthalten ist. Die Familie aus Baltimore bot erstmals einen Hinweis dafür, daß das I‐Antigen genetisch determiniert ist
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