Constructing orthogonal pandiagonal Latin squares and panmagic squares from modular n‐queens solutions

In this article, we show how to construct pairs of orthogonal pandiagonal Latin squares and panmagic squares from certain types of modular n‐queens solutions. We prove that when these modular n‐queens solutions are symmetric, the panmagic squares thus constructed will be associative, where for an n × n associative magic square A = (a_ij), for all i and j it holds that a_ij + an?i?1,n?j?1 = c for a fixed c. We further show how to construct orthogonal Latin squares whose modular difference diagonals are Latin from any modular n‐queens solution. As well, we analyze constructing orthogonal pandiagonal Latin squares from particular classes of non‐linear modular n‐queens solutions. These pandiagonal Latin squares are not row cyclic, giving a partial solution to a problem of Hedayat. © 2007 Wiley Periodicals, Inc. J Combin Designs 15: 221–234, 2007     

Structure of the asparagine-linked sugar chains of porcine kidney and human urine cerebroside sulfate activator protein

The specific sugar residues and their linkages in the oligosaccharides from pig kidney and human urine cerebroside sulfate activator proteins (saposin B), although previously hypothesized, have been unambiguously characterized. Exhaustive sequential exoglycosidase digestion of the trimethyl-p-aminophenyl derivatives, followed by either matrix-assisted laser desorption/ionization and/or mass spectrometry, was used to define the residues and their linkages. The oligosaccharides were enzymatically released from the proteins by treatment with peptidyl-N-glycosidase F and separated from the proteins by reversed-phase high-performance liquid chromatography (HPLC). Reducing termini were converted to the trimethyl-p-aminophenyl derivative and the samples were further purified by normal-phase HPLC. The derivatized carbohydrates were then treated sequentially with a series of exoglycosidases of defined specificity, and the products of each digestion were examined by mass spectrometry. The pentasaccharides from pig kidney and human urine protein were shown to be of the asparagine-linked complex type composed of mannose-alpha 1-6-mannose-beta 1-4-N-acetylglucosamine-N-acetylglucosamine(alpha 1-6-fucose). This highly degraded structure probably represents the final product of intra-lysosomal exoglycosidase digestion. Oligosaccharide sequencing by specific exoglycosidase degradation coupled with mass spectrometry is more rapid than conventional oligosaccharide sequencing. The procedures developed will be useful for sequencing other oligosaccharides including those from other members of the lipid-binding protein class to which cerebroside sulfate activator belongs. (c) 2000 John Wiley & Sons, Ltd.     

Phenylsulfonyl ene-allenes as efficient precursors to bicyclic systems via intramolecular [2 + 2]-cycloaddition reactions

Various phenylsulfonyl allene derivatives were prepared with double bonds tethered either to the alpha-position or the gamma-position of the allene. These substrates underwent a highly regio- and stereospecific thermal [2 + 2]-cycloaddition across the nonactivated cumulene double bond, forming distal cycloadducts (i.e., 57) in the case of alpha-tethered allenes and proximal adducts (i.e., 25) in the case of gamma-tethered allenes. The mechanistic rationale for the observed stereospecificity involves initial diradical formation, followed by a rapid ring closure to the more stable cis-fused ring system. The tether may be equipped with heteroatoms, allowing for the formation of fused heterocycles (e.g., 61), and the cycloaddition can be facilitated by the introduction of sterically bulky groups and/or by conformational rigidity to the tether. Other modes of cyclization were observed in the presence of sodium benzenesulfinate or Lewis acids, in which cases polar mechanisms prevail. The chemoselectivity is reversed for [4 + 2]-cycloadditions, which prefer instead to engage the vinyl sulfone moiety, independent of whether the tether is attached to the alpha- or gamma-position of the allene.     

Bicyclopentanoid sesquiterpenes. the synthesis of cedranoid sesquiterpenes via the photo-rearrangement of bicyclo[2.2.2]octenones

(±) - exo - 2,6,6 - Trimethyltricyclo[5.3.1.0^1,5]undecane - 8,10 - dione (11) has been synthesized from dimethyl 6,6 - dimethyl - 5 - oxobicyclo[2.2.2]oct - 7 - ene dicarboxylate (17). This constitutes a new synthesis of cedrol (3) since 11 has previously been converted to this compound.     

Isolation and structure of [HC[CH(SiMe(3))(SnMe(3))](2)](+): a remarkably stable sec-alkyl cation

The reaction of the tin-substituted propene Me3Sn(R)CHCH=CHR (R = SiMe3) with MCl4 in dichloromethane in the presence of Me3SnCl gives the first examples of isolable sec-alkyl carbocation salts, [HC{CH(R)SnMe3}2]+M2Cl9- (M = Zr, Hf). The compounds are thermally stable and, unlike previously isolated trialkyl carbocations, do not require superacidic media or weakly coordinating anions for stability. The crystal structure and DFT calculations suggest polarization of the Sn substituents and hyperconjugation as the reason for the unexpected stability. The stabilizing effect of tin is significantly stronger than that of Si. The carbocations are effective initiators for the polymerization of isobutene, isoprene, and alpha-methylstyrene.     

The separation of molybdenum valencies by paper chromatography part II1

The preparation of Mo^VI oxinate and a purported Mo^V oxine complex is described. The latter was analysed, and a number of its properties, including separation from the Mo^VI compound by paper chromatography, were studied.The preparation of a solution containing trivalent molybdenum and the separation of this valency from the pentavalent state by chromatography upon cellulose is also described.Suggestions as to the stability of thiocyanate and oxine compounds of Mo^III were made from the results of some extraction experiments performed upon trivalXnt molybdenum solutions.     

Enhancement of phosphoprotein analysis using a fluorescent affinity tag and mass spectrometry

A fluorescent affinity tag (FAT) was synthesized and was utilized to selectively modify phosphorylated serine and threonine residues via beta-elimination and Michael addition chemistries in a 'one-step' reaction. This labeling technique was used for covalent modification of both phosphoproteins and phosphopeptides, allowing identification of these molecular species by fluorescence imaging after solution- or gel-based separation methods. In addition to the strong fluorescence of the rhodamine tag, a commercially available antibody can be used to enrich low-abundance post-labeled phosphopeptides present in complex mixtures. Application of this methodology to phosphorylation-site mapping has been evaluated for a phosphoprotein standard, bovine beta-casein. Initial results demonstrated low femtomole detection limits after fluorescence image analysis of FAT-labeled proteins or peptides.