Hopanoids of methylotropic acetobacteria

Squalene, 35-methoxyho-6-ene-32R,33R,34S-triol, hop-22(29)-ene, and hopan-22-ol have been isolated fromAcetobacter sp. VSB 917. The structures of the substances isolated and of the 35-methoxyhop-6-ene-32R,33R,34S-triol triacetate obtained have been established by IR, mass, and¹H and¹³C NMR spectroscopies.Vitaminy Scientific-Production Association, Moscow. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 367–372, May–August, 1992.     

Determination of platinum and gold in biological materials by neutron activation analysis

A procedure for platinum and gold determination utilizing, neutron activation combined with radiochemical separation, has been developed. The reaction¹⁹⁸Pt (n, )¹⁹⁹ is used for Pt determination. Four procedures for gold separation are examined: (1) adsorption on untreated polyurethane foam (UPF). (2) extraction with dibutyl sulphide. (3) reduction of gold to elementary state in conc. H₂SO₄, and extraction of gold as diethyldithiocarbamate complex. The extraction with Cu(DDC)₂ is chosen as the most suitable process and applied to platinum and gold determinations in Bowen's Kale and mice organs, previously treated with Biocisplatinum^® specimens.     

Assembly of the inorganic double helix Mg6(Et2NCO2)12 by fixation of carbon dioxide: crystal and solution structure

The homoleptic magnesium carbamato complex Mg6(Et2NCO2)12, 1 (Et2NCO2- = diethylcarbamato anion), was prepared by the reaction of dibutylmagnesium with diethylamine, followed by carboxylation using gaseous carbon dioxide. Crystallographic characterization demonstrated that 1 has the standard M6(R2NCO2)12 structure and is a double helix of MgO(x)(x = 5, 6) coordination polyhedra with Delta or Lambda stereochemistry arising from the configuration around the six-coordinate Mg2+ cations. It crystallized in the orthorhombic space group Ccca with two molecules of Delta1 and two of Lambda1 per unit cell (a = 21.548 A, b = 25.094 A, c = 15.4485(11) A, alpha = beta = gamma = 90 degrees ). Extensive solution characterization of 1 by 1-dimensional proton and 13C NMR spectroscopy and by two-dimensional 1H-[13C] NMR correlation techniques verified that the helical structure is maintained in solution. Moreover, these measurements indicated that the intramolecular dynamics of 1 relating to motions of the ethyl groups was substantially hindered in solution. Correlation of the crystallographic and NMR structural studies indicated that this arises from a combination of hindered rotation about the carbamato C-N bond and efficient packing of the ethyl groups around the Mg6O24 core. The result is an inverted-micelle-like structure for 1 in which the hydrophobic ethyl groups form a sheath largely restricting access to the hydrophilic Mg6O24 core.     

Organic Synthesis and Technetium-99m Labeling of Some Amino-Phenol Ligands

We reported the synthesis and labeling of one tetradentate and two pentadentate amino-phenol ligands with technetium-99m by the direct pertechnetate addition and by ligand exchange methods. Labeling by direct pertechnetate addition was attended by adding pertechnetate eluate to the ethanolic solution of the amino-phenol ligands at pH 9. Stannous chloride dihydrate was used as reducing agent. Exchange studies were carried out via the use of the following ^99mTc-chelates: ^99mTc-DTPA, ^99mTc-gluconate, ^99mTc-tartrate and ^99mTc-citrate complexes. Ligand exchange method was achieved by incubation the ligand solutions with ^99mTc-co-ligands complexes in 0.05M bicarbonate buffer pH 9. At this pH value the ^99mTc-co-ligands dissociated and the more stable new ^99mTc-ligands were formed with high radiochemical yield 95%. The radiochemical yield of ^99mTc-labeled amino-phenol ligands were estimated by solvent extraction, electrophoresis and HPLC methods. The produced technetium-99m amino-phenol complexes were neutral, lipophilic and stable during the period of 24 hours.     

Peloruside A: a potent cytotoxic macrolide isolated from the new zealand marine sponge Mycale sp

A novel, polyoxygenated, pyranose ring containing 16-membered macrolide peloruside A (1) exhibiting cytotoxic activity in the nanomolar range was isolated from the New Zealand marine sponge Mycale sp. The structure of 1 and relative stereochemistry of the 10 stereogenic centers were determined on a 3 mg sample using a variety of spectroscopic methods. Compound 1 was isolated along with the previously reported cytotoxins mycalamide A (2) and pateamine (3) from a single specimen of this sponge.     

The Mukaiyama-Michael reaction of N-acyl-2,3-dihydro-4-pyridones: regio- and stereoselective synthesis of cis-2,6-disubstituted 1,2,5,6-tetrahydropyridines

[formula: see text] A convenient regio- and stereoselective preparation of 1,2,5,6-tetrahydropyridines of the type 1 has been developed, starting from readily available N-acyl-2,3-dihydro-4-pyridones 2.     

The possibility of different time scales in the dynamics of pore imbibition

To model the imbibition of liquids into porous solids, use is often made of the Lucas-Washburn equation, which relates the distance of penetration of a liquid at a given time to the pore radius, the viscosity and surface tension of the liquid, and the effective contact angle between the liquid and the solid. In this paper, we extend previous large-scale molecular dynamics simulations to show how this tool can be used to study the details of liquid imbibition, including the impact of the contact angle on the dynamics of penetration and the evolution of the internal flow field. In particular, we show that the asymptotic behavior of the contact angle versus time for a completely wetting liquid is given by approximately t(-1/4).     

Tuning the acceptors in catalyzed cyclizations initiated by allenes. Silylstannylation/cyclization of allene-aldehydes for synthesis of polyalkylated indolizidines including 223A congeners

Starting from succinamide and 1,2-heptadiene-4-ol, a racemic allene-aldehyde substrate, 20, suitable for R(3)SiSnR'(3)-mediated cyclization was synthesized in six steps and in 21% yield. Stereoselective cyclization (relative cis configuration at the new stereogenic centers of the homoallyl alcohol generated) proceeded smoothly, giving a mixture of indolizidinols bearing five contiguous stereocenters in a combined yield of 80%. Relative configurations of each of the products were unequivocally established by a combination of 2D NMR experiments and single-crystal X-ray analysis. The major indolizidinol obtained in 32% yield was elaborated into indolizidine 5,8-epi-indolizidine 223A via a five-step reaction sequence in 32% overall yield. The second major component (24%) of the key cyclization yielded, in four steps, indolizidine 6,8-epi-223 in 14% yield. Even though revision of the initially postulated structure foiled our original synthetic plans for the natural product, indolizidine 223A, the new stereoselective cyclization strategy and several selective transformations of the indolizidine derivatives reported here may find further applications for the synthesis of highly alkylated indolizidine and other related alkaloids.     

Gas-phase structures and mass spectra of binary pentafluorides

Most known non-radioactive pentafluorides have been examined by molecular-beam mass spectrometry and by the deflection of molecular beams in inhomogeneous electric fields. Extensive association of the vapors occurs for all but the lighter pentafluorides and the interhalogens. The interhalogen pentafluorides are strongly polar, consistent with the accepted C_4v symmetry. The transition-metal and Group V pentafluorides are all non-polar, except VF₅ and CrF₅ for which temperature-dependent polarity is observed. However, uncertainty exists as to whether these observations are applicable to monomeric pentafluorides in all cases. Mass-spectral cracking patterns are presented for all species.     

Investigation on the chemistry of berbans—VII: Synthesis of 10,11-dimethoxy(depyrrolo)raunescine stereoisomers

Acyloxy-ketone rearrangement, proceeding by the action of base, has been observed in the case of ketone 2. By the reduction of ketones 2 and 3 with sodium boron hydride, new 10, 11-dimethoxy(depyrrolo)raunescine stereoisomers (5a–7a) have been prepared. Previously known alcohols with alloberban skeleton (12,13) have been similarly converted into tetracyclic raunescine stereoisomers (8a,9) by the oxido-reductive method. The stereochemistry of these compounds has been investigated by physical (¹H NMR, IR) and by chemical methods.