Phosphorus-containing podands

A number of monopodands havingo-diphenylphosphinyl terminal groups were synthesized by alkylating sodium derivatives of oligoethylene glycols witho-(bromomethyl)phenyldiphenylphosphine. The stability constants of the complexes of these ligands with alkali metal cations at 25 °C were determined conductometrically in a THF—chloroform solution (41, v/v). The complexing ability of monopodands with respect to the cations studied increases monotonically as the number of electron-donating sites increases (from 3 to 8) for all of the cations except Li⁺ and, to some extent, Na⁺. In the case of Li⁺ a smooth decrease in the stability of the complexes is observed. The monopodands obtained in this work differ drastically in this regard from their structural isomers, bis[o-(diphenylphosphinylmethyl)phenyl] ethers of oligoethylene glycols, which had been studied previously.For part 10, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 952–956, May, 1993.     

Structure of 2H-3,4-dihydro-3-phenyl-3-oxo-1,5,3-benzodioxaphosphepine

Conclusions The seven-membered heterocycle in 2H-3,4-dihydro-3-phenyl-3-oxo-1,5,3-benzodioxaphosphepine was found to have twist conformation by x-ray diffraction structural analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskya, No. 5, pp. 1150–1152, April, 1989.     

Chemical fourling on the unit cell level as a structure-building operation in the solid state

Chemical fourling on the unit-cell level is introduced as a structure-building operation in the solid state. A chemical fourling structure is achieved when two twin planes are perpendicular to each other. Each fourling unit has infinite extension in only one direction and can be related to a well-known structure type or packing of atoms. The structures of the tetragonal tungsten bronzes M_xWO₃ and Pd(NH₃)₄Cl · H₂O are presented as examples of chemical fourlings of cubic close packing. The structures of SeO₂, Mn₂Hg₅, and Zr₂F₇O are shown to be a sequence of chemical fourlings of primitive cubic packing. Chemical fourling units of hexagonal close packing are found in the structures of tetragonal Ti₃Sb, α-V₃S and Sb₆O₇(SO₄)₂. The structures of CuAl₂, SeTl, NbTe₄, Ti₃Sb, and MnU₆ all have the same chemical fourling unit. Cr₂₃C₆ is described as a bounded chemical fourling of cubic close packing.     

Molecular and crystal structure of 2-phenoxy-2λ5-2,2′(3H,3′H)-spirobi[1,3,2-benzoxazaphosphole]

The crystal and molecular structure of 2-phenoxy-2⁵-2,2(3H,3H)-spirobi[1,3,2-benzoxazaphosphole] has been determined using X-ray diffraction structure analysis. The P atom in the molecule in question has a distorted trigonal bipyramidal coordination, with the bond lengths P-O_ax=1.701(1) and 1.700(1) Å, P-O_eq (Ph)=1.625 Å, P-N_eq=1.654(2) and 1.645(1) Å, and bond angles (O-P-O)_ax=175.69(7)° and (N-P-N)_eq = 132.38(7)°.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 876–879, May, 1993.     

Synthesis of H (type 4) trisaccharide,key structural fragment of globo-H and fucosyl-GM1 cancer-associated antigens

A convenient synthesis of Fucα1-2Galβ1-3GalNAcβ-OCH₂CH₂CH₂NH₂ (trisaccharide H type 4) is described. This glycan is the terminal part of glycosphingolipids globo-H and fucosyl-GM1 known as cancer-associated carbohydrate antigens.     

Favourable biospecific reactivity of blood group B antigenic trisaccharide chemically attached to poly-N-(2-hydroxyethyl)acrylamide-coated porous glass.

Blood group B antigenic trisaccharide-beta-aminopropyl glycoside (B-TSAP) covalently attached to poly-N-(2-hydroxyethyl)acrylamide-coated porous glass interacts with anti-B monoclonal antibodies faster than the ligand coupled to CNBr-activated Sepharose 4B and Affi-Gel 10. Rates of hydrophobic adsorption of antibodies on the butyl derivatives of the same supports were measured to evaluate the diffusion input to overall kinetics. The lowest average affinity adsorption time [t1(aff) = 250 s] observed for polymer-coated glass probably arises because of the flexibility of the extended segments of chemisorbed N-substituted polyacrylamide acting as effective spacer arms.     

Differences in reactivity of N-acetyl- and N,N-diacetylsialyl chlorides caused by their different supramolecular organization in solutions

O-Sialylation of a substituted indolin-3-one under phase-transfer catalysis conditions, which does not occur when N-acetylsialyl chloride is used, proceeds with N,N-diacetylsialyl chloride as the glycosyl donor. A study using dynamic light scattering of solutions of both sialyl chlorides under conditions close to the conditions used for glycosylation showed a difference in the correlation radii of light scattering particles in such solutions. This suggests that the introduction of an additional N-acetyl group into the sialyl chloride significantly alters the structure of the supramers of glycosyl donor, which apparently have an increased accessibility of individual molecules for the attack by a nucleophile, which increases its reactivity.

     

Two new long-period structures related to β-alumina

Two new ordered forms of “β-alumina” with rhombohedral symmetry have been discovered and their structures deduced from one-dimensional electron microscope images of thick crystals. Referred to a hexagonal cell, their lattice parameters are a = 5.59Å, c = 169.5Å and a = 5.59Å, c = 339Å. A symbolism for describing structures related to that of β-alumina is proposed.     

Effect of a catechol segment in a polyether chain on the complexing ability of some phosphonate and quinoline monopodands

The complexing ability of monopodands with o-diethoxyphosphinylmethoxyphenyl and 8-quinoline end groups, containing both ethylene glycol and catechol units in the polyether chain, was studied by conductimetry in tetrahydrofuran-CHCl₃. Replacement of ethvlene glycol by catechol changes the efficiency insignificantly, but in a number of cases leads to some increase in K/Li and k/Na selectivity of phosphonate podands, and the K/Li and Na/Li selectivity of quinoline podands.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2611–2615, November, 1989.     

Comparison of water-soluble CdTe nanoparticles synthesized in air and in nitrogen

It is commonly believed that high-quality CdTe nanoparticles with strong luminescence can only be prepared under the protection of an inert gas such as nitrogen or argon. Here, we report the preparation of highly luminescent CdTe nanoparticles in air and compare their luminescence properties with CdTe nanoparticles made in nitrogen. We find that both water-soluble CdTe nanoparticles made in air and in nitrogen exhibit strong photoluminescence as well as upconversion luminescence at room temperature. However, differences do exist between the particles made in air and those made in nitrogen. In particular, the particles prepared in air display a faster growth rate, grow to larger sizes, and display stronger electron coupling relative to the particles prepared in nitrogen. X-ray photoelectron spectroscopy analysis indicates that the oxygen content in the nanoparticles synthesized in air is higher that that in particles synthesized in N(2), likely resulting in a higher availability of excess free cadmium. Cytotoxicity measurements reveal that the particles made in air appear slightly more toxic, possibly due to the excess of free cadmium.