Synthesis of (±)-biotin from a substituted 2,3-dehydrothiophane

(±)-Biotin has been synthesized from a mixture of cis- and allo-trisubstituted dehydrothiophanes by a scheme providing for the easy elimination of the accompanying allo-substituted thiophane in the form of an intermediate and not as the final isomeric allo-biotin. The imidazoline ring of biotin is formed from a dialkoxy-carbonyldiaminothiophane under the conditions of partial hydrolysis of one of the protective groups with the elimination of phosgene from the scheme of synthesis.All-Union Scientific-Research Vitamin Institute, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 220–223, March–April, 1981.     

Origin of the lower critical flocculation temperature in polymer colloids stabilized by polydimethylsiloxane

Summary It has recently been reported (6, 7) that poly(methyl methacrylate) particles that are sterically stabilised by polydimethylsiloxane flocculate on cooling when dispersed in short chain n-alkanes. Since the LCFT was reported to be essentially independent of the nature of the dispersion medium, it was postulated (2) that incipient flocculation of these particles was caused by crystallisation of the polydimethysiloxane chains, which would have allowed the attractive van der Waals forces to become operative. This hypothesis has now been confirmed by low temperature X-ray studies.

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Zusammenfassung Von (6, 7) wurde kürzlich mitgeteilt, daß Poly(methylmethacrylat)-Teilchen, die mit Polydimethylsiloxan sterisch stabilisiert sind, in kurzkettigenn-Alkanen als Dispersionsmittel ausflocken. Da die LCFT im wesentlichen unabhängig von der Natur des Dispersionsmediums ist, wurde von (2) angenommen, daß die beginnende Ausflockung dieser Teilchen auf eine Kristallisation der Polydimethylsiloxan-Ketten zurückzuführen ist, bedingt durch die wirkenden van der Waals-Anziehungskräfte. Diese Hypothese wurde nun durch Röntgenuntersuchungen bei tiefer Temperatur bestätigt.

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FLUORESCENCE SPECTRA IN LUNG WITH PORPHYRIN INJECTION

The fluorescence emission spectra from human bronchial mucosa and tumors, before and after injection of dihematoporphyrin ether/ester, have been measured with an optical multichannel analyzer from 500 to 750 nm. Fluorescence was excited with a violet krypton ion laser (average wavelength 410 nm). The autofluorescence spectra decrease monotonically with increasing wavelength except for a small broad peak near 600 nm. The spectra from tumor sites, after injection of the fluorescent porphyrin, exhibit the characteristic fluorescence emission at 630 and 690 nm, added to the autofluorescence spectrum. The spectra from control or nontumor sites are similar but the magnitude of the component due to the injected porphyrin is smaller than at a tumor site. The magnitude ratio of tumor to control site fluorescence depends on concentration of the porphyrin, tumor thickness, and time after injection. Autofluorescence degrades contrast and thus makes very thin tumors difficult to image. Subtraction of the autofluorescence background is desirable.     

Freezing temperatures and densities of solutions of some hydrocarbons and sodium oleate inN-methylacetamide. Evidence for a solvophobic interaction

The freezing temperatures and densities (at 31°C) of solutions of octane, nonane, decane, 3,3-diethylpentane, and sodium oleate inN-methylacetamide (NMA) have been measured. The molality of the freezing solution was calculated from the density. The solubilities of octane, nonane, and decane inN-methylacetamide are also reported. Apparent molal volumes calculated from the densities are close to the values in the pure hydrocarbons and are not strong functions of the concentration. This indicates the absence of any unusual packing effect. The calculated free energies of transfer of the hydrocarbons from pure hydrocarbon to NMA solution are much less negative than the corresponding values for water, showing that the bulk solvophobic interaction inN-methylacetamide is smaller than in water. This is consistent with the freezing temperatures of sodium oleate which show that micelles do not form below 0.1 mole-kg^–1. The osmotic coefficients of the hydrocarbons calculated from the freezing temperatures showed negative deviations from ideality that were larger for the hydrocarbons with the higher molecular weights. Two estimates of the pairwise solvophobic interaction inN-methylacetamide indicate that it is also smaller than in water. The solvophobic effect in this solvent does not include the large entropy and enthalpy effects found in aqueous solutions.     

S=N versus S+-N-: an experimental and theoretical charge density study

To elucidate the bonding situation in the widely discussed hypervalent sulfur nitrogen species, the charge density distributions rho(r) and related properties of four representative compounds, methyl(diimido)sulfinic acid H(NtBu)(2)SMe (1), methylene-bis(triimido)sulfonic acid H(2)C[S(NtBu)(2) (NHtBu)](2) (2), sulfurdiimide S(NtBu)(2) (3), and sulfurtriimide S(NtBu)(3) (4), were determined experimentally by high-resolution low-temperature X-ray diffraction experiments (T = 100 K). This set of molecules represents an ideal frame of reference for the comparison of SN bonding modes, because they contain short formal S=N double bonds as well as long S-N single bonds, some of them influenced by inter- or intramolecular hydrogen bonds. For comparison, the gas-phase ab initio calculations of the four model compounds, H(NMe)(2)SMe, H(2)C[S(NMe)(2)(NHMe)](2), S(NMe)(2), and S(NMe)(3), were performed. The topological features were found to be not particularly sensitive with respect to different substituents R (R = H, Me, tBu). In this paper, it is documented that theory and experiment differ in the eigenvalues of the Hessian matrix because of systematically differing positions of the bond critical points but agree very well concerning the spatial Laplacian distribution and the distinct polarization of all investigated sulfur-nitrogen bonds. Both recommend the S(+)-N(-) formulation of sulfur nitrogen bonds in 1 and 2 since all nitrogen atoms are found to be sp(3) hybridized. The planar SNx (x = 2, 3) units in the diimide 3 and the triimide 4 reveal characteristics of m-center-n-electron systems. For none of the investigated S-N bonds, a classical double bond formulation can be supported. This is further substantiated by the NBO/NRT approach. Valence expansion to more than eight electrons at the sulfur atom can definitely be excluded to explain the bonding.